Synthesis, characterization and crystal structures of 2-[(E)-2-(4-hydroxy-3,5-dimethylphenyl)-1-diazenyl]benzoic acid and its polymeric and monomeric triorganotin(IV) complexes

Abstract

Three triorganotin(IV) complexes of composition R 3SnLH (R = Me, Bu and Ph and LH = 2-[(E)-2-(4-hydroxy-3,5-dimethylphenyl)-1-diazenyl]benzoate) have been synthesized and characterized by 1H, 13C, 119Sn NMR, and IR spectroscopic techniques in combination with elemental analysis. The crystal structures of the carboxylate ligand HO 2CC 6H 4{N N(C 6H 2-4-OH-3,5-(CH 3) 2)}- o in its neutral form and three triorganotin(IV) complexes, viz., polymeric (R 3Sn[O 2CC 6H 4{N–N(H)(C 6H 2-4-O-3,5-(CH 3) 2)}- o]) n (R = Me ( 1) and Bu ( 2)) and monomeric Ph 3Sn[O 2CC 6H 4{N–N(H)(C 6H 2-4-O-3,5-(CH 3) 2)}- o] ( 3) complexes are reported. The polymeric complexes 1 and 2 exist as extended chains in which the LH-bridged Sn-atoms adopt a trans-R 3SnO 2 trigonal bipyramidal configuration with R groups in the equatorial positions and the axial sites occupied by an oxygen atom from the carboxylate ligand and the phenoxide O atom of the next carboxylate ligand. The Sn atom in complex 3 has a distorted tetrahedral geometry. In all three complexes, the carboxylate ligand is in the zwitterionic form with the phenolic proton moved to the nearby azo nitrogen atom, in contrast to the free carboxylic acid ligand which is in the azo form.