Dibutyltin(IV) complexes of the 5-[(E)-2-(Aryl)-1-diazenyl]-2-hydroxybenzoic acid ligand:: an investigation of structures by X-ray diffraction, solution and solid state tin NMR, electrospray ionisation MS and assessment of in vitro cytotoxicity

A series of dibutylbis 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoatoltin(TV) complexes, Bu(2)Sn(LH)(2), have been prepared and characterized by (1)H, (13)C, (119)Sri NMR and ESI mass spectrometry in solution. The structures of the complexes Bu(2)Sn(L(1)H)(2) (1), Bu(2)Sn(L(3)H)(2) (3), Bu(2)Sn(L(4)H)(2) (4), and Bu(2)Sn(L(6)H)(2) (6) (L = 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoate: aryl = phenyl (L(1)H), 3-methylphenyl (L(3)H), 4-methylphenyl (L(4)H) and 4-bromophenyl (L(6)H)) were determined by X-ray crystallography and (117)Sn CP-MAS NMR spectroscopy in the solid state. In general, the complexes were found to adopt a skew-trapezoidal bipyramidal arrangement around the tin atom. In addition, there are weak bridging intermolecular Sn(...)O contacts in complexes 1 and 3, but not in 4 and 6, where one of the hydroxy oxygen atoms from a neighboring molecule coordinates weakly with the Sn atom, thereby completing a seventh coordination site in the extended Sn coordination sphere. The Sn(...)O distance is 3.080(2) and 3.439(2) Angstrom in 1 and 3, respectively, which are significantly shorter than the sum of the van der Waals radii of the Sn and O atoms (similar to3.8 Angstrom). In 1, this Sn(...)O interaction links the molecules into polymeric chains. In 3, these interactions link pairs of molecules into head-to-head dimeric units. The in vitro cytotoxicity of compound 2 indicates better results than cisplatin and etoposide against seven well characterized human tumor cell lines. (C) 2004 Elsevier B.V. All rights reserved.