Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties.

In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ2N,N')bis(µ-3-phenylprop-2-enoato-κ3O,O':O)calcium(II)], [Ca(C10H7O2)2(C10H8N2)]n, (1), and poly[(1,10-phenanthroline-κ2N,N')(µ3-3-phenylprop-2-enoato-κ4O:O,O':O')(µ-3-phenylprop-2-enoato-κ3O,O':O)barium(II)], [Ba(C10H7O2)2(C10H8N2)]n, (2), and characterized them by FT-IR and UV-Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C-H...O hydrogen bonds and π-π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297-1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

A novel three-dimensional SrII coordination polymer based on benzene-1,2,4,5-tetracarboxylate: hydrothermal synthesis, crystal structure and spectroscopic and thermal studies.

Coordination of the anions of benzenecarboxylic acids with metal cations leads to coordination polymers with various structural features. Very few examples of strontium-based structures have been reported. A new three-dimensional coordination polymer, namely poly[aqua(µ12-benzene-1,2,4,5-tetracarboxylato)distrontium(II)], [Sr2(C10H2O8)(H2O)]n, has been synthesized under hydrothermal conditions and characterized by thermal analysis, vibrational spectroscopy (Raman and IR), single-crystal X-ray diffraction and powder X-ray diffraction. The coordination geometries around the two independent SrII ions can be described as a distorted dodecahedron and a distorted monocapped square antiprism. The compound features a three-dimensional structure containing inorganic motifs, with two-dimensional layers connected through organic linkers, and possesses a topologic structure of a binodal (6,12) connected alb net with the Schläfli symbol {415}2{448.618}. The final product of thermal decomposition is strontium oxide (SrO).

catena-Poly[bis(1,3-benzo-thia-zol-3-ium) [[di-chlorido-anti-monate(III)]-di-µ-chlorido-µ-oxido-[chlorido-anti-monate(III)]-µ-chlorido]].

The title compound, {(C7H6NS)2[Sb2Cl6O]} n , contains two benzo-thia-zolidium cations and one tri-µ-chlorido-tri-chlorido-µ-oxido-di-anti-monate(III) anion. The structure of the inorganic cation may be described as as being built up from two polyhedra, i.e. a square-pyramidal SbCl4O and a distorted octa-hedral SbOCl5 unit, sharing a common face (comprising the O atom and two Cl atoms). The two benzo-thia-zole cations are quasi-planar and subtend a dihedral angle of 19.93 (5)°. The crystal packing can be described by alternating (100) layers and [001] chains of the organic cations and inorganic anions connected through an extensive three-dimensional network of N-H⋯Cl, C-H⋯O and C-H⋯Cl hydrogen bonds. This is consolidated by slipped π-π stacking, with centroid-to-centroid distances between the benzo-thia-zole rings of 3.7111 (18)-3.8452 (16) Å. These inter-actions link the mol-ecules within the layers and also link the layers together and reinforce the cohesion of the ionic structure.

Crystal structure of cis-tetra-aqua-dichlorido-cobalt(II) sulfolane disolvate.

In the title compound, [CoCl2(H2O)4]·2C4H8SO2, the Co(II) cation is located on the twofold rotation axis and is coordinated by four water mol-ecules and two adjacent chloride ligands in a slightly distorted octa-hedral coordination environment. The cisoid angles are in the range 83.27 (5)-99.66 (2)°. The three transoid angles deviate significantly from the ideal linear angle. The crystal packing can be described as a linear arrangement of complex units along c formed by bifurcated O-H⋯Cl hydrogen bonds between two water mol-ecules from one complex unit towards one chloride ligand of the neighbouring complex. Two solvent mol-ecules per complex are attached to this infinite chain via O-H⋯O hydrogen bonds in which water mol-ecules act as the hydrogen-bond donor and sulfolane O atoms as the hydrogen-bond acceptor sites.

Crystal structure of 3-carbamo-thio-yl-pyridinium thio-cyanate.

In the cation of the title salt, C6H7N2S(+)·SCN(-), the C=S bond is oriented trans with respect to the C-C=N fragment in the pyridine ring. The planes of the aromatic ring and the thio-amide fragment of the cation make a dihedral angle of 38.31 (4)°. In the crystal, the components are linked by N-H⋯S and N-H⋯N, hydrogen bonds, forming a two-dimensional network parallel to (10-1).

catena-Poly[[trans-bis-(1,3-benzo-thia-zole-κN)manganese(II)]-di-µ-chlorido].

In the title coordination polymer, [MnCl2(C7H5NS)2] n , the Mn(II) ion is located on the inter-section of a twofold rotation axis and a mirror plane and adopts an octa-hedral coordination geometry defined by two mutually trans N atoms from benzo-thia-zole ligands which occupy the axial positions, and four Cl atoms which form the equatorial sites. The Mn(II) ions are connected by two bridging Cl atoms, forming chains parallel to the c axis. The crystal packing can be descibed as alternating layers parallel to (001) featuring π-π stacking inter-actions with a centroid-centroid distance of 3.6029 (15) Å.

Bis(4-amino-benzene-sulfonamide-κN (4))di-chlorido-zinc.

In the title compound, [ZnCl2(C6H8N2O2S)2], the Zn(II) ion lies on a twofold rotation axis and has a slightly distorted tetra-hedral coordination geometry, involving two Cl atoms and two N atoms from the amino groups attached directly to the benzene rings [Zn-Cl = 2.2288 (16) Šand Zn-N = 2.060 (5) Å]. The dihedral angle between the benzene rings is 67.1 (3)°. The crystal packing can be describe as layers in a zigzag arrangement parallel to (001). The amine H atoms act as donor atoms and participate in inter-molecular N-H⋯O and N-H⋯Cl hydrogen bonds, forming a three-dimensional network.

2,2'-(Disulfanedi-yl)dianilinium dichloride dihydrate.

In the title hydrated mol-ecular salt, C12H14N2S2 (2+)·2Cl(-)·2H2O, the dihedral angle between the benzene rings in the dication is 9.03 (17)° and the C-S-S-C torsion angle is 96.8 (2)°. The crystal packing can be described as alternating organic and anionic water layers lying parallel to (100), which are linked by N-H⋯Cl and N-H⋯O hydrogen bonds. O-H⋯Cl hydrogen bonds and aromatic π-π stacking inter-actions [centroid-centroid separation = 3.730 (3) Å] are also observed.

2-(2-Nitro-phenyl-sulfin-yl)acetonitrile.

In the title compound, C8H6N2O3S, the dihedral angle between the nitro group and the benzene ring is 6.76 (9)°. The bond-angle sum at the S atom is 308.1°. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds to generate (010) sheets. The crystal studied was found to be a racemic twin.

1-Chloro-methyl-sulfinyl-2-nitro-benzene.

In the title compound, C(7)H(6)ClNO(3)S, the nitro group forms a dihedral angle of 2.7 (4)° with the benzene ring. The bond-angle sum at the S atom is 303.7°. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds, forming layers lying parallel to (-101).