Organotin(IV) complexes derived from Schiff base N'-[(1E)-(2-hydroxy-3-methoxyphenyl)methylidene]pyridine-4-carbohydrazone: synthesis, in vitro cytotoxicities and DNA/BSA interaction.

Five organotin(IV) compounds were synthesized from N'-[(1E)-(2-hydroxy-3-methoxyphenyl)methylidene]pyridine-4-carbohydrazone and the corresponding dialkyltin(IV) or trialkyltin(IV) precursor. Solid state structures were determined by IR, elemental analysis, NMR spectroscopy, and for 1, 2, 4 and 5 single crystal X-ray diffraction analysis. Compounds 1, 2 and 4 are monomers with the tin atoms five-coordinated in distorted trigonal bipyramid, of which the deprotonated Schiff base ligand chelate to tin center in the enolic tridentate mode. Differently, in compound 5, the enolization does not occur for the Schiff base ligand, and only the pyridinyl N atom and the deprotonated phenol hydroxyl oxygen atom participate in the coordination. Fascinatingly, six trimethyltin(IV) coordination units are linked by the Sn⋯N weak interaction atoms and form a 72-membered crown-like macrocycle. Preliminary in vitro cytotoxicity studies on five human tumor cells lines (HL-60, A549, HT-29, HCT-116 and Caco-2) by MTT assay reveal that di-n-butyltin(IV) complex 2 and diphenyltin(IV) complex 4 triggered significant antiproliferative effects in cultured tumor cells, and their cytotoxic activity correlates with intracellular organotin(IV) concentration. The interaction of the complexes with calf thymus DNA (CT-DNA) has been explored by absorption and emission titration methods, which revealed that complexes 2 and 4 interact with CT-DNA through groove-binding and partial intercalation of the extended planar ligand with the DNA base stack. Further, the albumin interactions of complexes 2 and 4 were investigated using fluorescence quenching spectra and synchronous fluorescence spectra. Studies reveal that di-n-butyltin(IV) complex 2 with higher cytotoxicity show stronger DNA/BSA interaction than diphenyltin(IV) complex 4.

Iodido-bis-(morpholine-4-carbodi-thio-ato-κ(2) S,S')(1,10-phenanthroline-κ(2) N,N')bis-muth(III).

The title compound, [Bi(C4H8NOS2)2I(C12H8N2)], is monomeric, with the Bi(III) atom chelated by the two S atoms of two morpholine-4-carbodi-thio-ate ligands and the two N atoms of a 1,10-phenanthroline ligand. An iodide ligand completes the coordination sphere, with the seven-coordinate Bi(III) atom adopting a highly distorted monocapped octa-hedral geometry.

Novel tetranuclear triarylantimony(V) complexes with (±)-mandelic acid ligands: synthesis, characterization, in vitro cytotoxicity and DNA binding properties.

Four novel tetranuclear organoantimony(V) complexes [R3SbL]4, in which LH = (±)-mandelic acid and R = phenyl (1), 4-fluorophenyl (2), 3-fluorophenyl (3), 3,4,5-trifluorophenyl (4), were synthesized and characterized. The complexes displayed rapid, low micromolar in vitro cytotoxicity against a range of epithelial tumour cells and efficient CT-DNA binding.

Synthesis, structural characterization and in vitro cytotoxicity of diorganotin (IV) diimido complexes.

Reactions of the diorganotin with two N-OH diimide ligands (N-hydroxyphthalimide and N-hydroxysuccinimide) yielded five new dimeric tetraorganostannoxanes formulated as R(8)Sn(4)O(2)L(2)X(2). The crystal structures of the complexes reveal the formation of the tetranuclear species contains a planar Sn(4)O(4) core, consisting of three adjacent rhombs with bridging oxo and N-OH diimide ligands. The central tin atoms are five-coordinated to assume a distorted trigonal bipyramidal configuration and the N-OH diimide ligands act as monodentate O-bound planar. In vitro cytotoxic activities of the title compounds have been determined against three cell lines (A549, HCT-8 and HL-60). Studies reveal that three di-n-butyltin(IV) diimido complexes show higher cytotoxic activities than cisplatin. The structure-activity relationship of the cytotoxicity of the title complexes has also been discussed.

Bis(N-benzoyl-N-phenyl-hydroxy-l-aminato-κO,O')dimethyl-tin(IV).

The Sn atom in the title compound, [Sn(CH(3))(2)(C(13)H(10)NO(2))(2)], has a highly distorted octa-hedral coordination with the equatorial plane made up of four O atoms from two N-benzoyl-N-phenyl-hydroxy-laminate ligands and the axial positions occupied by two methyl groups. The crystal structure is stabilized by van der Waals inter-actions.

[5-Chloro-2-hy-droxy-N'-(2-oxidobenzyl-idene)benzohydrazidato]dimethyl-tin(IV).

In the title compound, [Sn(CH(3))(2)(C(14)H(9)ClN(2)O(3))], the Sn(IV) ion is coordinated by one N and two O atoms from the tridentate 5-chloro-2-hy-droxy-N'-(2-oxidobenzyl-idene)benzohydrazidate (L) ligand and two methyl groups in a distorted trigonal-bipyramidal geometry. In the ligand, the hy-droxy group is involved in an intra-molecular O-H⋯N hydrogen bond and the two aromatic rings form a dihedral angle of 5.5 (1)°. In the crystal, weak inter-molecular C-H⋯O hydrogen bonds and π-π inter-actions between the aromatic rings [centroid-centroid distance = 3.816 (3) Å] link the mol-ecules into centrosymmetric dimers.

catena-Poly[[trimethyl-tin(IV)]-µ-3,5-difluoro-benzoato-κO:O'].

In the title compound, [Sn(CH(3))(3)(C(7)H(3)F(2)O(2))](n), the central Sn atom is coordinated by two O atoms from the anion and three methyl C atoms in a polymeric fashion owing to the presence of bidentate bridging carboxyl-ate ligands. The five-coordinate Sn atom exists in a distorted trigonal-bipyramidal geometry with the mol-ecules connected by weak C-H⋯F inter-moleclar inter-actions, forming supra-molecular chains parallel to [010].

Bis(acetohydroxamato-κO,O')diphenyl-tin(IV).

The complex mol-ecule of the title compound, [Sn(C(6)H(5))(2)(C(2)H(4)NO(2))(2)], has crystallographically imposed twofold symmetry. The Sn atom is coordinated by four O atoms from two acetohydroxamate ligands and by two C atoms from phenyl groups in a distorted octa-hedral geometry. In the crystal, mol-ecules are connected by N-H⋯O hydrogen-bonding inter-actions, forming a chain structure along the c axis.

N-Hy-droxy-pyridine-4-carboxamide.

The title compound, C(6)H(6)N(2)O(2), is approximately planar with an r.m.s. deviation for the non-H atoms of 0.052 Å. In the crystal, a two-dimensional array in the bc plane is stabilized by O-H⋯N and N-H⋯O hydrogen bonds.

3-Hy-droxy-N'-[(E)-3-pyridyl-methyl-idene]-2-naphtho-hydrazide.

The title compound, C(17)H(13)N(3)O(2), displays an E configuration about the C=N bond. The mean planes of the pyridine and benzene rings make a dihedral angle of 31.2 (2)°. An intra-molecular O-H⋯O hydrogen bond is observed. In the crystal, inter-molecular N-H⋯N hydrogen bonding links the mol-ecules into a chain along [101].

(E)-4-[2-(2-Hy-droxy-benzo-yl)-hydra-zin-ylidene]penta-noic acid.

The title mol-ecule, C(12)H(14)N(2)O(4), adopts a trans configuration with respect to the C=N double bond. The amino group is involved in an intra-molecular N-H⋯O hydrogen bond. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into doubled sheets parallel to the (101) plane.

(µ-2,3-Dibromo-succinato-κO:O)bis-[methano-lato-κO)triphenyl-anti-mony(V)].

In the title mol-ecule, [Sb(2)(C(6)H(5))(6)(C(4)H(4)Br(2)O(4))(CH(3)O)(2)], two [Sb(CH(3)O)Ph(3)](+) units are linked by the two carboxyl-ate O atoms of a meso-2,3-dibromo-succinate bridging ligand, forming a dinuclear compound. The Sb(IV) atom is five-coordinated in a slightly distorted trigonal-bipyramid geometry by phenyl C atoms in the equatorial positions and two O atoms in the axial positions. C-H⋯O inter-actions link the mol-ecules into a two-dimensional network parallel to (010). The -CH- group of the centrosymmetric 2,3-dibromosuccinate anion is disordered over two sites in a 0.6:0.4 ratio.

{1-[(2-Oxidonaphthalen-1-yl)methylidene]thiosemicarbazidato-κN,O,S}diphenyl-tin(IV).

The asymmetric unit of the title compound, [Sn(C(6)H(5))(2)(C(12)H(9)N(3)OS)], contains two independent mol-ecules with almost identical configurations. In each mol-ecule, the Sn(IV) atom is coordinated by O, N and S atoms from a (2-oxido-1-naph-thaldehyde)-thio-semicarbazonato ligand and two C atoms from phenyl rings in a distorted trigonal-bipyramidal geometry. Weak inter-molecular N-H⋯O and N-H⋯S hydrogen bonds link four mol-ecules into a centrosymmetric tetra-mer. The crystal packing exhibits short inter-molecular S⋯S contacts of 3.335 (3) Å.

Di-µ-methanolato-κO:O-bis[tri-chlorido(dimethyl-formamide-κO)tin(IV)].

The title compound, [Sn(2)(CH(3)O)(2)Cl(6)(C(3)H(7)NO)(2)], contains two hexa-coordinated Sn(IV) atoms symmetrically bridged by two deprotonated methanol ligands, with an inversion center in the middle of the planar Sn(2)O(2) ring. The other sites of the distorted octa-hedral coordination geometry of the Sn(IV) atom are occupied by three Cl atoms and one O atom from a dimethyl-formamide mol-ecule. The complex mol-ecules are connected by weak C-H⋯Cl hydrogen bonds into a two-dimensional supra-molecular network parallel to (10).

Bis(µ-chloroacetato-κO:O')bis(chloro-acetato-κO)di-µ(3)-oxido-tetrakis[dibenzyl-tin(IV)].

The title tetra-nuclear complex mol-ecule, [Sn(4)(C(7)H(7))(8)(C(2)H(2)ClO(2))(4)O(2)], has crystallographically imposed inversion symmetry. Each Sn atom has a distorted trigonal-bipyramidal geometry, with the equatorial plane formed by an oxido O atom and two C atoms of two benzyl anions. The configuration of the complex is stabilized by a pair of C-H⋯O hydrogen bonds. In the crystal, complex mol-ecules are linked into zigzag chains along [110] by C-H⋯O hydrogen bonds.

Bis(µ-3,5-difluorobenzoato)bis[(3,5-di-fluorobenzoato)dimethyltin(IV)].

In the dinuclear title complex, [Sn(2)(CH(3))(4)(C(7)H(3)F(2)O(2))(4)], the Sn(IV) atom is chelated by two 3,5-difluoro-benzoate (dfb) anions and coordinated by two methyl groups while an O atom from the adjacent dfb anion bridges the Sb atom with a longer Sb-O bond distance of 2.793 (4) Å. The complex mol-ecule has 2 symmetry and the Sn(IV) atom is in a distorted penta-gonal-bipyramidal coordination geometry. In the crystal, mol-ecules are connected by C-H⋯O and C-H⋯F hydrogen bonds.

3-Hy-droxy-N'-[(E)-2-thienyl-methyl-idene]-2-naphtho-hydrazide.

The asymmetric unit of the title compound, C(16)H(12)N(2)O(2)S, contains three independent mol-ecules. Intra-molecular N-H⋯O hydrogen bonds in the three mol-ecules lead to very similar conformations: the thio-pene ring and naphthalene ring system in the three mol-ecules form dihedral angles of 10.3 (2), 9.1 (2) and 9.3 (3)°. In the crystal structure, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into chains propagating in [031].

Bis(cyclohexylammonium) 2,2'-disulfanediyldibenzoate.

In the title molecular salt, 2C(6)H(14)N(+)·C(14)H(8)O(4)S(2) (2-), the complete dianion is generated by crystallographic twofold symmetry and a twisted conformation is found [the C-S-S-C torsion angle is 87.13 (2)° and the dihedral angle between the rings is 83.4 (2)°]. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the cations and anions.

Synthesis, Characterization, and Crystal Structure of a Diorganotin(IV) Complex with 2-Oxo-2-Phenylacetic Acid 4-Hydroxybenzohydrazone.

The complex dibutyltin 2-oxo-2-phenylacetic acid 4-hydroxybenzohydrazone has been synthesized and characterized by elemental analysis, IR, (1)H and (13)C NMR, and X-ray single-crystal diffraction studies. The crystal structure belongs to triclinic, space group P-1 with a = 9.3220 (10) Å, b = 9.8779 (11) Å, c = 15.9401 (17) Å, ß = 97.0930 (10)°, Z = 2, V = 1427.6(3) Å(3), Dc = 1.413 mg/cm(3), µ = 0.936 mm(-1), F(000) = 628, R = 0.1158, and wR = 0.2522. X-ray analysis indicates that O(2), N(2), O(4), and O(4)#1 from the ligand and O(5) from ethanol molecule are in the equatorial positions; the axial positions are occupied by two n-butyl groups. It shows a distorted pentagonal bipyramid configuration with seven-coordination for central tin atom. Fascinatingly, the supramolecular infrastructures are observed, which exist as two-dimensional sheets assembled from the organometallic subunits through intermolecular and intramolecular O-H⋯X or C-H⋯X (X = O or N) hydrogen bonds.

Octa-kis(2-chloro-benz-yl)di-µ(2)-hydroxido-di-µ(3)-oxido-bis-(2-phenyl-acetato)tetra-tin(IV).

The asymmetric unit of the title compound, [Sn(4)(C(7)H(6)Cl)(8)(C(8)H(7)O(2))(2)O(2)(OH)(2)], comprises one-half of the centrosymmetric tin(IV) complex. µ(3)-Oxide and µ(2)-hydroxide bridges link the four five-coordinate Sn(IV) atoms to generate three fused four-membered Sn-O-Sn-O rings in a ladder-like structure. The two endocyclic Sn atoms each bind to two µ(3)-oxide anions and a µ(2)-hydroxide ligand, together with two 2-chloro-benzyl groups. The exocyclic Sn atoms each carry a monodentate phenyl-acetate ligand, two 2-chloro-benzyl groups, and µ(3)-oxide and µ(2)-hydroxide ligands. Both types of Sn atoms adopt a distorted trigonal-bipyramidal coordination geometry. The mol-ecular conformation is stabilized by intra-molecular O-H⋯O inter-actions involving the µ(2)-hydroxide ligands and the C=O group of the phenyl-acetate ligand.