Synthesis and characterization of triorganotin(IV) complexes of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids.: Crystal and molecular structures of a series of triphenyltin 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoates (aryl=phenyl, 2-methylphenyl, 3-methylphenyl and 4-methoxyphenyl)

Abstract

The triphenyltin and tri-n-butyltin complexes of some 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids have been synthesized and characterized by 1H-, 13C-, 119Sn-NMR, IR and 119mSn Mössbauer spectroscopic techniques in combination with elemental analysis. The crystal structures of triphenyltin 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoates (aryl=phenyl, 2-methylphenyl, 3-methylphenyl and 4-methoxyphenyl) are reported. Both X-ray and 119Sn Mössbauer data indicate that the triphenyltin complexes adopt a monomeric distorted tetrahedral configuration with the carboxylate ligand coordinating in a monodentate mode. By contrast, 119Sn Mössbauer spectroscopy shows that each tributyltin complex is polymeric and features a trans-trigonal bipyramidal geometry with a planar SnBu3 unit and two apical carboxylate oxygen atoms derived from bidentate bridging carboxylate ligands. This is a solid-state effect, as both 119Sn-NMR and 1J(13C–119/117Sn) coupling constant data indicate tetrahedral geometries in solution for the triphenyl and tri-n-butyl complexes.