Synthesis and crystal structure of a heterobimetallic cadmium-sodium complex of 1,3,5-triazine-2,4,6-trione, [CdNa2(C3H2N3O3)4(H2O)8].

Heterobimetallic crystals of a cadmium-sodium complex of 1,3,5-triazine-2,4,6-trione, namely, µ-aqua-1:2κ2 O:O-hepta-aqua-1κ3 O,2κ2 O,3κ2 O-bis-(µ-4,6-dioxo-1,4,5,6-tetra-hydro-1,3,5-triazin-2-olato)-1:2κ2 O 2:N 1;2:3κ2 N 1:O 2-bis-(4,6-dioxo-1,4,5,6-tetra-hydro-1,3,5-triazin-2-olato)-1κO 2,3κO 2-2-cadmium-1,3-disodium, [CdNa2(C3H2N3O3)4(H2O)8], were grown by the single gel diffusion technique. The asymmetric unit of the title compound comprises four 1,3,5-triazine-2,4,6-trione ligands, two sodium atoms and one cadmium atom. Of the four ligands, two are monodentately coordinated to two Na atoms. The third ligand is coordinated bidentately to one Na and the Cd atom and the fourth is also coordinated bidentately to the Cd atom and the other Na atom. All the metal atoms are six-coordinate with a distorted octa-hedral geometry. The water mol-ecules bridge the Na atoms, constructing coordination polymer chains along the a axis and hence are linked by two Cd and one Na coordinations through the cyanuric acid ligands present in the coordination polymer chains, generating a two-dimensional coordination polymer in the (110) plane. The polymer formation is further assisted by means of many inter-molecular and intra-molecular N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds between the water mol-ecules and the ligands.

Crystal structure of 2-[(2E)-2-methyl-3-phenyl-prop-2-en-1-yl-idene]-N-phenyl-hydrazinecarboxamide.

The title compound, C17H17N3O, crystallizes with two independent mol-ecules in the asymmetric unit. The semicarbazone moieties of these independent mol-ecules (I and II) are essentially planar [maximum deviation of 0.042 (1) Šin mol-ecule I and 0.041 (1) Šin mol-ecule II], with the terminal phenyl rings twisted away from the mean plane of the semicarbazone moiety, making dihedral angles of 60.26 (8) and 28.76 (9)° in mol-ecule I and 31.07 (9) and 35.45 (8)° in mol-ecule II. The mol-ecules both exhibit an E configuration with respect to the C=C and azomethine C=N bonds. In the crystal, two classical N-H⋯O hydrogen-bonding inter-actions are present between the two mol-ecules, forming a centrosymmetric dimer, while a weak C-H⋯O non-classical hydrogen-bonding inter-action, with a donor-acceptor distance of 3.476 (2) Å, inter-connects two neighbouring centrosymmetric dimers to form a cage-like structure. These cage structures are inter-connected by weak C-H⋯π inter-actions with an H⋯π distance of 2.790 Å, forming supra-molecular chains along the c-axis direction.

Crystal structure of poly[[di-µ3-acetato-tetra-aqua-bis-(µ2-cyclo-hexane-1,4-di-carboxyl-ato)dilanth-an-um(III)] dihydrate].

The title compound, {[La2(CH3COO)2(C8H10O4)2(H2O)4]·2H2O} n or [La2(ac)2(e,a-cis-1,4-chdc)2(H2O)4]·2H2O, where ac is acetate and 1,4-chdc is cyclo-hexane-1,4-di-carboxyl-ate anion, is a binuclear lanthanum(III) complex. Each metal atom is deca-coordinated by four O atoms from two distinct 1,4-chdc2- ligands, four O atoms from three acetate groups and two O atoms from coordinated water mol-ecules to form a distorted bicapped square-anti-prismatic geometry. Two non-coordinated water mol-ecules are also present in the formula unit. The most remarkable feature of this compound is that it possesses a only cis conformation for cyclo-hexane-1,4-di-carb-oxy-lic acid, although the raw material consists of a mixture of cis and trans isomers. The µ3-η2:η2 coordination mode of the bridging acetate group and the flexible di-carboxyl-ate fragments of 1,4-chdc2- results in the formation of infinite two-dimensional lanthanide-carboxyl-ate layers within the crystal structure. The directionality of strong inter-molecular O-H⋯O and weak C-H⋯O inter-actions provides robustness to the layers, which leads to the construction of a three-dimensional supra-molecular network. The crystal studied was refined as a two-component twin.

Crystal structures of (1E,4E)-1,5-bis-(5-bromo-thio-phen-2-yl)-2,4-di-methyl-penta-1,4-dien-3-one and (E)-4-(5-bromo-thio-phen-2-yl)-1,3-di-phenyl-but-3-en-2-one.

The title compounds, C15H12Br2OS2, (I), and C20H15BrOS, (II), were synthesized by employing Claisen-Schmidt condensation of pentan-3-one and di-benzyl-acetone with 5-bromo-thio-phene-2-carbaldehyde in the presence of methano-lic KOH. Even though 1:2 products were expected in both of the reactions, 1:2 and 1:1 products were obtained as (I) and (II), respectively. In (I), the two methyl groups are trans to each other, 29.5 (7) and 28.7 (7)° away from the central carbonyl bond between them, whereas the two phenyl rings of di-benzyl-acetone subtend a dihedral angle of 53.09 (18)°. In the crystal of (I), C-H⋯O hydrogen bonds define mol-ecular chains along c. A second type of mol-ecular chain is formed along b by means of C-Br⋯π inter-actions. These two families of mol-ecular chains are stacked by π-π inter-actions, forming a three-dimensional supra-molecular architecture. In (II), similar C-H⋯O hydrogen bonds as in (I) define inversion dimers, whilst C-H⋯.π inter-actions build a staircase structure along the a axis.

Crystal structure of N'-[(E)-3,5-di-chloro-2-hy-droxy-benzyl-idene]-4-nitro-benzo-hydrazide di-methyl-formamide monosolvate.

In the title compound, C14H9Cl2N3O4·C3H7NO, the hydrazone mol-ecule adopts an E conformation with respect to azomethine bond, and the dihedral angle between the two aromatic rings [8.96 (11)°] shows that the rings are almost co-planar. The planar conformation of the mol-ecule is stabilized by the intra-molecular O-H⋯N hydrogen bond involving the OH group and azomethine N atom. The azomethine and keto bond distances [1.269 (2) and 1.210 (2) Å, respectively] are very close to the formal C=N and C=O bond lengths. The di-methyl-formamide solvent mol-ecule is connected to the hydrazone NH group via an N-H⋯O hydrogen bond. In the crystal, non-classical C-H⋯O and C-H⋯Cl hydrogen bonds link the mol-ecules into chains along [322]. A supra-molecular three-dimensional architecture is created by weak C-Cl⋯π [4.163 (3) Å, 83.26 (9)°] and π-π [centroid-centroid distance = 4.0395 (14) Å] inter-actions.

Crystal structure of (E)-N'-(5-bromo-2-hy-droxy-benzyl-idene)nicotinohydrazide monohydrate.

In the title compound, C13H10BrN3O2·H2O, the conformation about the azomethine double bond is E. The mol-ecule exists in the amido form with a C=O bond length of 1.229 (2) Å. There is an intra-molecular O-H⋯N hydrogen bond forming an S(6) ring motif. The whole mol-ecule is almost planar, with an r.m.s. deviation of 0.021 Šfor all non-H atoms, and the dihedral angle between the planes of the pyridine and benzene rings is 0.74 (12)°. In the crystal, the water mol-ecule of crystallization links the organic mol-ecules via Ow-H⋯O, Ow-H⋯N and N-H⋯Ow hydrogen bonds and short C-H⋯Ow contacts, forming sheets lying parallel to (100). Within the sheets there is a weak π-π inter-action involving the pyridine and benzene rings [centroid-to-centroid distance = 3.8473 (15) Å]. The sheets are linked via C-H⋯Br inter-actions, forming a three-dimensional network.

Crystal structure of (E)-2-[(2-hy-droxy-4-meth-oxy-phen-yl)(phen-yl)methyl-idene]-N-phenyl-hydrazine-1-carboxamide.

The title compound, C21H19N3O3, has an E conformation about the azomethine double bond. The central moiety of the hydrazinecarboxamide moiety [-N-N-C(=O)-N-] has an almost coplanar arrangement [maximum deviation for the C atom = 0.010 (2) Å]. This central moiety is flanked by three aromatic rings and its mean plane makes dihedral angles of 24.7 (1), 72.91 (12) and 34.26 (11) Å, respectively, with the phenolic ring, the phenyl ring attached to the same C atom as the phenolic ring, and the phenyl-hydrazine ring. The adjacent phenolic and phenyl rings are twisted away from each other to reduce steric hindrance and make a dihedral angle of 80.59 (12)°. The phenolic and phenyl-hydrazine rings are inclined to one another by 28.89 (11)°. The rigidity of the mol-ecule is increased by an intra-molecular O-H⋯N hydrogen bond involving the phenolic hydrogen and the azomethine N atom. In the crystal, the carbonyl O atom forms bifurcated hydrogen bonds with the two NH atoms of the hydrazinic group, leading to the formation of chains propagating along [001]. Within the chains there are also C-H⋯O hydrogen bonds present. The chains are linked via C=O⋯π [3.4316 (18) Å] and parallel slipped π-π inter-actions, involving inversion-related benzene rings [centroid-centroid distance = 3.8850 (14) Å; inter-planar distance = 3.3895 (10) Å; slippage = 1.899 Å], forming sheets lying parallel to (100).

Crystal structure of aqua-[(E)-N'-(5-bromo-2-oxido-benzyl-idene-κO)benzohydrazidato-κ(2) O,N']dioxidomolybdenum(VI) di-methyl-formamide monosolvate.

The title compound, [Mo(C14H9BrN2O2)O2(H2O)]·C3H7NO, has a distorted octa-hedral geometry around the Mo atom, with the two terminal oxide groups lying cis to each other. The two aromatic rings present in the mol-ecule are almost coplanar, forming a dihedral angle of 1.4 (2)°. The five-membered ring involving the metal atom is puckered, with an amplitude Q = 0.358 (2) Šand ϕ = 204.1 (6)°. In the crystal, pairs of inversion-related mol-ecules are linked by O-H⋯N hydrogen bonds. An O-H⋯O hydrogen bond connects the water ligand to the di-methyl-formamide solvent mol-ecule. The crystal packing also features π-π [centroid-centroid distance of 3.688 (2) Å] and C-H⋯O inter-actions.

Crystal structure of 4-{(E)-[2-(pyridin-4-ylcarbon-yl)hydrazin-1-yl-idene]meth-yl}phenyl acetate monohydrate.

The asymmetric unit of the title compound, C15H13N3O3·H2O, comprises a 4-{(E)-[2-(pyridin-4-ylcarbon-yl)hydrazinyl-idene]meth-yl}phenyl acetate mol-ecule and a solvent water mol-ecule linked by O-H⋯O and O-H⋯N hydrogen bonds from the water mol-ecule and a C-H⋯O contact from the organic mol-ecule. The compound adopts an E conformation with respect to the azomethine bond and the dihedral angle between the pyridine and benzene rings is 21.90 (7)°. The azomethine bond [1.275 (2) Å] distance is very close to the formal C=N bond length, which confirms the azomethine bond formation. An extensive set of O-H⋯O, O-H⋯N, N-H⋯O and C-H⋯O hydrogen bonds builds a two-dimensional network progressing along the c axis.

Crystal structure of 8-[7,8-bis-(4-chloro-benzo-yl)-7H-cyclo-penta-[a]ace-naphthylen-9-yl]naphthalene-1-carb-oxy-lic acid.

The title compound, C40H22Cl2O4, was formed by a Michael-Aldol domino reaction sequence, which coupled acenaphthene-quinone with 4-chloro-aceto-phenone in the presence of KOH in methanol. The dihedral angles between the central cyclo-penta-[a]ace-naphthyl-ene fused-ring system (r.m.s. deviation = 0.066 Å) and the 4-chloro-benzoyl rings are 62.25 (10) and 70.19 (10)°. The dihedral angle between the central ring system and the naphthoic acid grouping is 62.46 (7)°. This twisting of the pendant rings facilitates the formation of an intra-molecular aromatic π-π stacking inter-action between the 4-chloro-benzoyl and naphthoic acid rings, with centroid-centroid distances of 3.4533 (16) and 3.5311 (16) Å, and a C-H⋯π inter-action between one of the H atoms of the central moiety and the 4-chloro-benzoyl ring with an H⋯π distance of 2.57 Å. In the crystal, carb-oxy-lic acid inversion dimers generate R 2 (2)(8) loops. The dimers are linked by weak C-H⋯O and C-H⋯Cl hydrogen bonds and C-H⋯π inter-actions, generating a three-dimensional architecture.

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: crystal structure of a novel sulfur bridged copper(II) box-dimer.

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined.

Crystal structure of (4-chloro-phen-yl)[2-(10-hy-droxy-phenanthren-9-yl)phenanthro[9,10-b]furan-3-yl]methanone.

In the title compound, C37H21ClO3, the dihedral angle between the two phenanthrene moieties is 57.79 (5)°. The furan and one of the phenanthrene groups are fused in an almost coplanar arrangement [dihedral angle = 5.14 (8)°] and the furan unit makes dihedral angles of 70.27 (11) and 57.58 (8)° with the planes of the phenyl and the second phenanthrene group, respectively. In the crystal, neighbouring mol-ecules are connected via two inter-molecular hydrogen-bonding inter-actions (O-H⋯O and C-H⋯O) towards the carbonyl O atom with donor-acceptor distances of 2.824 (2) and 3.277 (3) Å, creating an inversion dimer. A non-classical C-H⋯Cl inter-action [3.564 (2) Å] and three C-H⋯π inter-actions, with C⋯π distances of 3.709 (3), 3.745 (2) and 3.628 (3) Å, connect the mol-ecules, forming a three-dimensional supra-molecular architecture in the solid state.

Crystal structure of 2-[(E)-4-benz-yloxy-2-hy-droxy-benzyl-idene]-N-cyclo-hexyl-hydrazinecarbo-thio-amide aceto-nitrile hemisolvate.

The asymmetric unit of the title compound, C21H25N3O2S·0.5C2H3N, contains two independent mol-ecules with almost similar structural properties along with a solvent mol-ecule of aceto-nitrile. The compound exists in the E conformation with respect to the azomethine C=N double bond. The hydrazinecarbo-thio-amide moieties in both independent mol-ecules are almost planar [maximum deviations of 0.013 (2) and 0.007 (2) Å]. The mol-ecular conformation is stabilized in each case by an intra-molecular N-H⋯N hydrogen bond. In the crystal, pairs of N-H⋯S hydrogen bonds link each of the independent mol-ecules into inversion dimers. The dimers are inter-connected by means of three C-H⋯π inter-actions.

Dichlorido{(2E)-2-[phen-yl(pyridin-2-yl)methyl-idene]hydrazinecarbo-thio-amide}cadmium(II) methanol monosolvate.

In the title compound, [CdCl2(C13H12N4S)]·CH3OH, the coord-ination geometry of the Cd(II) ion is slightly distorted square-pyramidal, as indicated by the τ index of 0.36 (8). The S atom, two N atoms from the pyridyl-azomethine moiety and one of the Cl atoms comprise the basal plane, while the other Cl atom occupies the apical position. The hydrazinecarbo-thio-amide moiety adopts an E conformation with respect to the azomethine bond. The solvate mol-ecule in the crystal lattice plays a major role in inter-connecting adjacent mol-ecules by means of O-H⋯Cl and N-H⋯O hydrogen-bonding inter-actions. A supra-molecular three-dimensional architecture is sustained in terms of further N-H⋯Cl and C-H⋯Cl hydrogen-bonding inter-actions.

Bis{µ-N-[(E)-4-benz-yloxy-2-oxidobenzyl-idene]-4-nitro-benzene-carbo-hydrazidato}bis-[di-aqua-nickel(II)] di-methyl-formamide tetra-solvate.

The molecule of the title complex, [Ni2(C21H15N3O5)2(H2O)4]·4C3H7NO, is located on an inversion centre. This results in a dimeric Ni(II) complex, with the two Ni(II) atoms bridged by phenolate O atoms. The tridentate ligand is chelated to each Ni(II) atom via one N and two O atoms of the imino-late form of the hydrazide moiety, which has the same conformation as the free ligand. The coordination geometry around each Ni(II) ion is slightly distorted octa-hedral. A supra-molecular three-dimensional architecture is created by dominant inter-molecular O-H⋯N, O-H⋯O and C-H⋯O hydrogen-bonding inter-actions. These are augmented by two C-H⋯π inter-actions and a π-π inter-action with a centroid-centroid distance of 3.681 (2) Å.

(2E,7E)-2,7-Bis[(thio-phen-2-yl)methyl-idene]cyclo-hepta-none.

The whole molecule of the title compound, C17H16OS2, is generated by two-fold rotational symmetry. The carbonyl C and O atoms of the cycloheptanone ring lie on the twofold rotation axis which bisects the opposite -CH2-CH2- bond of the ring. The mol-ecule exists in an E,E conformation with respect to the C=C double bond. The cyclo-hepta-none ring exhibits a twisted chair conformation and its mean plane makes a dihedral angle of 50.12 (19)° with the planes of the thio-phene rings. The two S atoms are in an anti arrangement with respect the carbonyl O atom and the dihedral angle between the two thio-phene ring planes is 69.38 (7)°. In the molecule, there are two intramolecular C-H⋯S hydrogen bond, forming S(6) ring motifs. In the crystal, inversion dimers are generated via pairs of C-H⋯O hydrogen bonds. These dimers are inter-connected by another inter-action of the same kind with a neighbouring mol-ecule, forming a mol-ecular chain along the c-axis direction.

N'-[(E)-1-(2-Fluoro-phen-yl)ethyl-idene]pyridine-4-carbohydrazide.

The title compound, C14H12FN3O, adopts an E conformation with respect to the azomethine bond. The pyridyl and fluoro-benzene rings make dihedral angles of 38.58 (6) and 41.61 (5)° respectively with the central C(=O)N2CC unit, resulting in a non-planar mol-ecule. The inter-molecular inter-actions comprise two classical N-H⋯O and N-H⋯N hydrogen bonds and four non-classical C-H⋯O and C-H⋯F hydrogen bonds. These inter-actions are augmented by a weak π-π inter-action between the benzene and pyridyl rings of neighbouring mol-ecules, with a centroid-centroid distance of 3.9226 (10) Å. This leads to a three-dimensional supra-molecular assembly in the crystal system. The F atom is disordered over two sites in a 0.559 (3): 0.441 (3) ratio, through a 180° rotation of the fluoro-benzene ring.

(2E)-2-Benzyl-idene-N-phenyl-hydrazinecarboxamide.

The mol-ecule of the title compound, C14H13N3O, adopts an E conformation with respect to the azomethine C=N bond, and is roughly planar, with an r.m.s. deviation of the non-H atoms from the least-squares plane of 0.100 (2) Šand a dihedral angle between the terminal benzene rings of 5.74 (12)°. An intramolecular N-H⋯N hydrogen bond closes an S(6) ring. In the crystal, mol-ecules are linked by the pairs of N-H⋯O hydrogen bonds into centrosymmetric dimers. Dimers related by translation along [010] form slanted stacks, the shortest C⋯C inter-molecular distance within the stack being 3.283 (3) Å. Weak C-H⋯π inter-actions link the stacks into a three-dimensional structure.

N'-[(E)-(3-Fluoro-pyridin-2-yl)methyl-idene]pyridine-3-carbohydrazide dihydrate.

The organic molecule in the title dihydrate, C12H9FN4O·2H2O, exists in the E conformation with respect to the azo-methane C=N double bond. The mol-ecule is approximately planar, with a maximum deviation of 0.117 (1) Šfor the carbonyl O atom from the mean plane of the mol-ecule. Both pyridine rings are essentially coplanar with the central C(=O)N2C unit [dihedral angles = 1.99 (7) and 5.71 (8)°], exhibiting a significant difference in dihedral angles from its benzohydrazide analogue. The crystal packing features N-H⋯O, O-H⋯N and O-H⋯O hydrogen-bond inter-actions, which lead to the formation of a chain along the c-axis direction through one of the water mol-ecules present, and these chains are stacked one over the other by means of π-π inter-actions [with centroid-centroid distances of 3.7099 (10) and 3.6322 (10) Å] between the aromatic rings in neighbouring anti-parallel mol-ecules, building a three-dimensional supra-molecular network.

(E)-2-(4-Benz-yloxy-2-hy-droxy-benzyl-idene)-N-methyl-hydrazinecarbo-thio-amide.

The mol-ecule of the title compound, C16H17N3O2S, adopts an E conformation with respect to the azomethine C=N bond. The hydrazinecarbo-thio-amide fragment is close to planar, with a largest deviation from the least-squares plane of 0.079 (2) Šfor the hydrazide N atom. This fragment forms a dihedral angle of 9.43 (9)° with the central benzene ring. The benzene rings are inclined to one another by 67.55 (12)°. The mol-ecular conformation is stabilized by an intra-molecular O-H⋯N hydrogen bond involving the azomethine N atom. In the crystal, mol-ecules are linked through weak N-H⋯S and N-H⋯O hydrogen bonds into double ribbons along [010]. The crystal packing also features C-H⋯π inter-actions.