The PtII atom in the title complex, [Pt(C15H18N4O4S)(C2H6OS)], exists within a square-planar NS2O donor set provided by the N, S, O atoms of the di-anionic tridentate thio-semicarbazo ligand and a dimethyl sulfoxide S atom. The two chelate rings are coplanar, subtending a dihedral angle of 1.51 (7)°. The maximum deviation from an ideal square-planar geometry is seen in the five-membered chelate ring with an S-Pt-S bite angle of 96.45 (2)°. In the crystal, mol-ecules are linked via N-H⋯O, C-H⋯O, C-H⋯N and C-H⋯π inter-actions into two-dimensional networks lying parallel to the ab plane. The conformations of related cyclo-hexyl-hydrazine-1-carbo-thio-amide ligands are compared to that of the title compound.
The crystal and mol-ecular structures of the title 1:2 co-crystal, C14H14N4O2·2C7H6O2, are described. The oxalamide mol-ecule has a (+)-anti-periplanar conformation with the 4-pyridyl residues lying to either side of the central, almost planar C2N2O2 chromophore (r.m.s. deviation = 0.0555 Å). The benzoic acid mol-ecules have equivalent, close to planar conformations [C6/CO2 dihedral angle = 6.33 (14) and 3.43 (10)°]. The formation of hy-droxy-O-H⋯N(pyrid-yl) hydrogen bonds between the benzoic acid mol-ecules and the pyridyl residues of the di-amide leads to a three-mol-ecule aggregate. Centrosymmetrically related aggregates assemble into a six-mol-ecule aggregate via amide-N-H⋯O(amide) hydrogen bonds through a 10-membered {⋯HNC2O}2 synthon. These are linked into a supra-molecular tape via amide-N-H⋯O(carbon-yl) hydrogen bonds and 22-membered {⋯HOCO⋯NC4NH}2 synthons. The contacts between tapes to consolidate the three-dimensional architecture are of the type methyl-ene-C-H⋯O(amide) and pyridyl-C-H⋯O(carbon-yl). These inter-actions are largely electrostatic in nature. Additional non-covalent contacts are identified from an analysis of the calculated Hirshfeld surfaces.
The asymmetric unit of the title co-crystal, C10H5BrO2·C14H8O4 [systematic name: 2-bromo-1,4-di-hydro-naphthalene-1,4-dione-1,8-dihy-droxy-9,10-di-hydro-anthracene-9,10-dione (1/1)], features one mol-ecule of each coformer. The 2-bromo-naphtho-quinone mol-ecule is almost planar [r.m.s deviation of the 13 non-H atoms = 0.060 Å, with the maximum deviations of 0.093 (1) and 0.099 (1) Å being for the Br atom and a carbonyl-O atom, respectively]. The 1,8-di-hydroxy-anthra-quinone mol-ecule is planar (r.m.s. deviation for the 18 non-H atoms is 0.022 Å) and features two intra-molecular hy-droxy-O-H⋯O(carbon-yl) hydrogen bonds. Dimeric aggregates of 1,8-di-hydroxy-anthra-quinone mol-ecules assemble through weak inter-molecular hy-droxy-O-H⋯O(carbon-yl) hydrogen bonds. The mol-ecular packing comprises stacks of mol-ecules of 2-bromo-naphtho-quinone and dimeric assembles of 1,8-di-hydroxy-anthra-quinone with the shortest π-π contact within a stack of 3.5760 (9) Å occurring between the different rings of 2-bromo-naphtho-quinone mol-ecules. The analysis of the Hirshfeld surface reveals the importance of the inter-actions just indicated but, also the contribution of additional C-H⋯O contacts as well as C=O⋯π inter-actions to the mol-ecular packing.
In the bis-chalcone mol-ecule of the title compound, C24H18O4·2C3H7NO, the central benzene and terminal hy-droxy-phenyl rings form a dihedral angle of 14.28 (11)° and the central C=C double bond adopts a trans configuration. In the crystal, the bis-chalcone and solvate mol-ecules are inter-connected via O-H⋯O hydrogen bonds, which were investigated by Hirshfeld surface analysis. Solid-state fluorescence was measured at λex = 4400 Å. The emission wavelength appeared at 5510 Å, which corresponds to yellow light and the solid-state fluorescence quantum yield (Ff) is 0.18.
In the title mol-ecular salt, 2C6H10N3O+·C8H4O42-, the N atom of each of the two 2-amino-4-meth-oxy-6-methyl-pyrimidine mol-ecules lying between the amine and methyl groups has been protonated. The dihedral angles between the pyrimidine rings of the cations and the benzene ring of the succinate dianion are 5.04 (8) and 7.95 (8)°. Each of the cations is linked to the anion through a pair of N-H⋯O(carboxyl-ate) hydrogen bonds, forming cyclic R22(8) ring motifs which are then linked through inversion-related N-H⋯O hydrogen bonds, giving a central R24(8) motif. Peripheral amine N-H⋯O hydrogen-bonding inter-actions on either side of the succinate anion, also through centrosymmetric R22(8) extensions, form one-dimensional ribbons extending along [211]. The crystal structure also features π-π stacking inter-actions between the aromatic rings of the pyrimidine cations [minimum ring centroid separation = 3.6337 (9) Å]. The inter-molecular inter-actions were also investigated using Hirshfeld surface studies and two-dimensional fingerprint images.
A new conjugated carbazole chalcone compound, (E)-3-[4-(9,9a-di-hydro-8aH-carbazol-9-yl)phen-yl]-1-(4-nitro-phen-yl)prop-2-en-1-one (CPNC), C27H18N2O3, was synthesized using a Claisen-Schmidt condensation reaction. CPNC crystallizes in the monoclinic non-centrosymmetric space group Cc and adopts an s-cis conformation with respect to the ethyl-enic double bonds (C=O and C=C). The crystal packing features C-H⋯O and C-H⋯π inter-actions whose percentage contribution was qu-anti-fied by Hirshfeld surface analysis. Quantum chemistry calculations including geometrical optimization and mol-ecular electrostatic potential (MEP) were analysed by density functional theory (DFT) with a B3LYP/6-311 G++(d,p) basis set.
2-(Benzo-furan-2-yl)-2-oxoethyl 2-chloro-benzoate, C17H11ClO4 (I), and 2-(benzo-furan-2-yl)-2-oxoethyl 2-meth-oxy-benzoate, C18H14O5 (II), were synthesized under mild conditions. Their chemical and mol-ecular structures were analyzed by spectroscopic and single-crystal X-ray diffraction studies, respectively. These compounds possess different ortho-substituted functional groups on their phenyl rings, thus experiencing extra steric repulsion force within their mol-ecules as the substituent changes from 2-chloro (I) to 2-meth-oxy (II). The crystal packing of compound (I) depends on weak inter-molecular hydrogen bonds and π-π inter-actions. Mol-ecules are related by inversion into centrosymmetric dimers via C-H⋯O hydrogen bonds, and further strengthened by π-π inter-actions between furan rings. Conversely, mol-ecules in compound (II) are linked into alternating dimeric chains propagating along the [101] direction, which develop into a two-dimensional plate through extensive inter-molecular hydrogen bonds. These plates are further stabilized by π-π and C-H⋯π inter-actions.
The title compound, [Sn(CH3)2(C5H8NOS2)2], has the Sn(IV) atom bound by two methyl groups which lie over the weaker Sn-S bonds formed by two asymmetrically chelating di-thio-carbamate ligands so that the coordination geometry is skew-trapezoidal bipyramidal. The most prominent feature of the mol-ecular packing are secondary Sn⋯S inter-actions [Sn⋯S = 3.5654 (7) Å] that lead to centrosymmetric dimers. These are connected into a three-dimensional architecture via methyl-ene-C-H⋯S and methyl-C-H⋯O(morpholino) inter-actions. The Sn⋯S inter-actions are clearly evident in the Hirshfeld surface analysis of the title compound along with a number of other inter-molecular contacts.
In the title di-thio-carbazate ester, C16H17N3S2 (systematic name: (Z)-{[(benzyl-sulfan-yl)methane-thio-yl]amino}[1-(6-methyl-pyridin-2-yl)ethyl-idene]amine), the central methyl-idenehydrazinecarbodi-thio-ate (C2N2S2) core is almost planar (r.m.s. deviation = 0.0111 Å) and forms dihedral angles of 71.67 (3)° with the approximately orthogonally inclined thio-ester phenyl ring, and 7.16 (7)° with the approximately coplanar substituted pyridyl ring. The latter arrangement and the Z configuration about the imine-C=N bond allows for the formation of an intra-molecular hydrazine-N-H⋯N(pyrid-yl) hydrogen bond that closes an S(6) loop. In the crystal, phenyl-C-H⋯S(thione), methyl-ene-C-H⋯π(pyrid-yl), methyl-ene- and phenyl-C-H⋯π(phen-yl) contacts connect mol-ecules into supra-molecular layers propagating in the bc plane; the layers stack along the a axis with no directional inter-actions between them. The analysis of the Hirshfeld surface indicates the relative importance of an intra-layer phenyl-H⋯H(pyrid-yl) contact upon the mol-ecular packing.
In the redetermination of the title compound, C3H5N2OS+·CI-, the asymmetric unit consists of one independent 2-oxo-1,3-thia-zolidin-4-iminium cation and one independent chloride anion. The cation inter-acts with a chloride anion via N-H⋯Cl hydrogen bonds forming a supra-molecular chain along [010]. These supra-molecular chains are further extended by weak C-H⋯Cl and C-H⋯O inter-actions, forming a two-dimensional network parallel to (001). The crystal structure is further stabilized by weak C-O⋯π inter-actions, supporting a three-dimensional architecture. The structure was previously determined by Ananthamurthy & Murthy [Z. Kristallogr. (1975). 8, 356-367] but has been redetermined with higher precision to allow the hydrogen-bonding patterns and supra-molecular inter-actions to be investigated.
In the racemic title mol-ecular salt, C17H17F6N2O+·C2ClF2O3- (systematic name: 2-{[2,8-bis-(tri-fluoro-meth-yl)quinolin-4-yl](hy-droxy)meth-yl}piperidin-1-ium chloro-difluoro-acetate), the cation, which is protonated at the piperidine N atom, has the shape of the letter, L, with the piperidin-1-ium group being approximately orthogonal to the quinolinyl residue [the Cq-Cm-Cm-Na (q = quinolinyl; m = methine; a = ammonium) torsion angle is 177.79 (18)°]. An intra-molecular, charge-assisted ammonium-N-H⋯O(hydrox-yl) hydrogen bond ensures the hy-droxy-O and ammonium-N atoms lie to the same side of the mol-ecule [Oh-Cm-Cm-Na (h = hydrox-yl) = -59.7 (2)°]. In the crystal, charge-assisted hydroxyl-O-H⋯O-(carboxyl-ate) and ammonium-N+-H⋯O-(carboxyl-ate) hydrogen bonds generate a supra-molecular chain along [010]; the chain is consolidated by C-H⋯O inter-actions. Links between chains to form supra-molecular layers are of the type C-Cl⋯π(quinolinyl-C6) and the layers thus formed stack along the a-axis direction without directional inter-actions between them. The analysis of the calculated Hirshfeld surface points to the dominance of F⋯H contacts to the surface (40.8%) with significant contributions from F⋯F (10.5%) and C⋯F (7.0%) contacts.
The title phosphanegold(I) thiol-ate compound, [Au(C9H9N2O3S)(C21H21P)], is a second monoclinic polymorph (space group P21/c) that complements a previously reported Cc polymorph [Broker & Tiekink (2008 ▸). Acta Cryst. E64, m1582]. An SP donor set defines an approximately linear geometry about the gold atom in both forms. The key distinguishing feature between the present structure and the previously reported polymorph rests with the relative disposition of the thiol-ate ligand. In the title compound, the orientation is such to place the oxygen atom in close contact with the gold atom [Au⋯O = 2.915 (2) Å], in contrast to the aryl ring in the original polymorph. In the crystal, linear supra-molecular chains along the a-axis direction mediated by C-H⋯π and nitro-O⋯π inter-actions are found. These pack with no directional inter-actions between them. The analysis of the Hirshfeld surfaces for both forms of [Au(C9H9N3O3S)(C21H21P)] indicates quite distinctive inter-action profiles relating to the differences in inter-molecular contacts found in their respective crystals.
The title compound, C16H15N5O2, adopts the shape of the letter L with the dihedral angle between the outer pyridyl rings being 78.37 (5)°; the dihedral angles between the central pyrazolyl ring (r.m.s. deviation = 0.0023 Å) and the methyl-ene-bound pyridyl and methyoxypyridyl rings are 77.68 (5) and 7.84 (10)°, respectively. Intra-molecular amide-N-H⋯N(pyrazol-yl) and pyridyl-C-H⋯O(amide) inter-actions are evident and these preclude the participation of the amide-N-H and O atoms in inter-molecular inter-actions. The most notable feature of the mol-ecular packing is the formation of linear supra-molecular chains aligned along the b-axis direction mediated by weak carbonyl-C=O⋯π(triazol-yl) inter-actions. An analysis of the calculated Hirshfeld surfaces point to the importance of H⋯H (46.4%), C⋯H (22.4%), O⋯H (11.9%) and N⋯H (11.1%) contacts in the crystal.
The asymmetric unit of the title 1:1 solvate, C14H14N4O2·C6H6 [systematic name of the oxalamide mol-ecule: N,N'-bis-(pyridin-4-ylmeth-yl)ethanedi-amide], comprises a half mol-ecule of each constituent as each is disposed about a centre of inversion. In the oxalamide mol-ecule, the central C2N2O2 atoms are planar (r.m.s. deviation = 0.0006 Å). An intra-molecular amide-N-H⋯O(amide) hydrogen bond is evident, which gives rise to an S(5) loop. Overall, the mol-ecule adopts an anti-periplanar disposition of the pyridyl rings, and an orthogonal relationship is evident between the central plane and each terminal pyridyl ring [dihedral angle = 86.89 (3)°]. In the crystal, supra-molecular layers parallel to (10) are generated owing the formation of amide-N-H⋯N(pyrid-yl) hydrogen bonds. The layers stack encompassing benzene mol-ecules which provide the links between layers via methyl-ene-C-H⋯π(benzene) and benzene-C-H⋯π(pyrid-yl) inter-actions. The specified contacts are indicated in an analysis of the calculated Hirshfeld surfaces. The energy of stabilization provided by the conventional hydrogen bonding (approximately 40 kJ mol-1; electrostatic forces) is just over double that by the C-H⋯π contacts (dispersion forces).
The mol-ecular structure of the title bis-pyridyl substituted di-amide hydrate, C14H14N4O2·H2O, features a central C2N2O2 residue (r.m.s. deviation = 0.0205 Å) linked at each end to 3-pyridyl rings through methyl-ene groups. The pyridyl rings lie to the same side of the plane, i.e. have a syn-periplanar relationship, and form dihedral angles of 59.71 (6) and 68.42 (6)° with the central plane. An almost orthogonal relationship between the pyridyl rings is indicated by the dihedral angle between them [87.86 (5)°]. Owing to an anti disposition between the carbonyl-O atoms in the core, two intra-molecular amide-N-H⋯O(carbon-yl) hydrogen bonds are formed, each closing an S(5) loop. Supra-molecular tapes are formed in the crystal via amide-N-H⋯O(carbon-yl) hydrogen bonds and ten-membered {⋯HNC2O}2 synthons. Two symmetry-related tapes are linked by a helical chain of hydrogen-bonded water mol-ecules via water-O-H⋯N(pyrid-yl) hydrogen bonds. The resulting aggregate is parallel to the b-axis direction. Links between these, via methyl-ene-C-H⋯O(water) and methyl-ene-C-H⋯π(pyrid-yl) inter-actions, give rise to a layer parallel to (10); the layers stack without directional inter-actions between them. The analysis of the Hirshfeld surfaces point to the importance of the specified hydrogen-bonding inter-actions, and to the significant influence of the water mol-ecule of crystallization upon the mol-ecular packing. The analysis also indicates the contribution of methyl-ene-C-H⋯O(carbon-yl) and pyridyl-C-H⋯C(carbon-yl) contacts to the stability of the inter-layer region. The calculated inter-action energies are consistent with importance of significant electrostatic attractions in the crystal.
In the title isonicotinohydrazide hydrate, C14H12BrN3O2·H2O {systematic name: N'-[(1E)-1-(5-bromo-2-hy-droxy-phen-yl)ethyl-idene]pyridine-4-carbohydrazide monohydrate}, the central CN2O region of the organic mol-ecule is planar and the conformation about the imine-C=N bond is E. While an intra-molecular hy-droxy-O-H⋯N(imine) hydrogen bond is evident, the dihedral angle between the central residue and the benzene rings is 48.99 (9)°. Overall, the mol-ecule is twisted, as seen in the dihedral angle of 71.79 (6)° between the outer rings. In the crystal, hydrogen-bonding inter-actions, i.e. hydrazide-N-H⋯O(water), water-O-H⋯O(carbon-yl) and water-O-H⋯N(pyrid-yl), lead to supra-molecular ribbons along the a-axis direction. Connections between these, leading to a three-dimensional architecture, are mediated by Br⋯Br halogen bonding [3.5366 (3) Å], pyridyl-C-H⋯O(carbon-yl) as well as weak π-π inter-actions [inter-centroid separation between benzene rings = 3.9315 (12) Å]. The Hirshfeld surface analysis reveals the importance of hydrogen atoms in the supra-molecular connectivity as well as the influence of the Br⋯Br halogen bonding.
In the title carbohydrazide, C10H7N3O4S, the dihedral angle between the terminal five-membered rings is 27.4 (2)°, with these lying to the same side of the plane through the central CN2C(=O) atoms (r.m.s. deviation = 0.0403 Å), leading to a curved mol-ecule. The conformation about the C=N imine bond [1.281 (5) Å] is E, and the carbonyl O and amide H atoms are anti. In the crystal, N-H⋯O hydrogen bonds lead to supra-molecular chains, generated by a 41 screw-axis along the c direction. A three-dimensional architecture is consolidated by thienyl-C-H⋯O(nitro) and furanyl-C-H⋯O(nitro) inter-actions, as well as π-π inter-actions between the thienyl and furanyl rings [inter-centroid distance = 3.515 (2) Å]. These, and other, weak inter-molecular inter-actions, e.g. nitro-N-O⋯π(thien-yl), have been investigated by Hirshfeld surface analysis, which confirms the dominance of the conventional N-H⋯O hydrogen bonding to the overall mol-ecular packing.
The asymmetric unit of the title compound, C13H11N3O2S2, comprises two independent mol-ecules (A and B); the crystal structure was determined by employing synchrotron radiation. The mol-ecules exhibit essentially the same features with an almost planar benzo-thia-zole ring (r.m.s. deviation = 0.026 and 0.009 Å for A and B, respectively), which forms an inclined dihedral angle with the phenyl ring [28.3 (3) and 29.1 (3)°, respectively]. A difference between the mol-ecules is noted in a twist about the N-S bonds [the C-S-N-N torsion angles = -56.2 (5) and -68.8 (5)°, respectively], which leads to a minor difference in orientation of the phenyl rings. In the mol-ecular packing, A and B are linked into a supra-molecular dimer via pairwise hydrazinyl-N-H⋯N(thiazol-yl) hydrogen bonds. Hydrazinyl-N-H⋯O(sulfon-yl) hydrogen bonds between A mol-ecules assemble the dimers into chains along the a-axis direction, while links between centrosymmetrically related B mol-ecules, leading to eight-membered {⋯HNSO}2 synthons, link the mol-ecules along [001]. The result is an undulating supra-molecular layer. Layers stack along the b-axis direction with benzo-thia-zole-C-H⋯O(sulfon-yl) points of contact being evident. The analyses of the calculated Hirshfeld surfaces confirm the relevance of the above inter-molecular inter-actions, but also serve to further differentiate the weaker inter-molecular inter-actions formed by the independent mol-ecules, such as π-π inter-actions. This is also highlighted in distinctive energy frameworks calculated for the individual mol-ecules.
The title compounds, C24H18O2 and C24H17FO2, were synthesized using the Claisen-Schmidt condensation method and characterized by UV-Vis spectroscopy. Weak inter-molecular C-H⋯O, C-H⋯π and π-π hydrogen-bonding inter-actions help to stabilize the crystal structures of both compounds. The geometrical parameters obtained from the mol-ecular structure were optimized using density functional theory (DFT) calculations at the B3LYP/6-311++G(d,p) level, showing a good correlation with the experimental results. The small HOMO-LUMO energy gaps of 3.11 and 3.07 eV enhances the non-linear responses of these mol-ecular systems.