Synthesis, characterization, and analysis of intermolecular interactions of isostructural diorganotin compounds containing enantiomeric 1,1-dithioligands

Abstract

The reaction of enantiomerically pure (+) and (−) menthol as well as (R)-(+)- and (S)-(−)N-benzyl-1-phenylethylamine with carbon disulfide in presence of potassium hydroxide yielded, respectively, chiral xanthate and dithiocarbamates as their potassium salts. These chiral 1,1-dithioligands were reacted with diphenyltin dihalides to produce four enantiomeric and isostructural pairs of diorganotin complexes of formula (+)-[SnPh2{xanMEN}Cl] (1), (−)-[SnPh2{xanMEN}Cl] (1m), (+)-[SnPh2{xanMEN}Br] (2), (−)-[SnPh2{xanMEN}Br] (2m), (+)-[SnPh2{dtcBPE}Cl] (3), (−)-[SnPh2{dtcBPE}Cl] (3m), (+)-[SnPh2{dtcBPE}Br] (4), and (−)-[SnPh2{dtcBPE}Br] (4m). The 119Sn{1H} NMR data and the X-ray single-crystal diffraction studies of the eight heteroleptic compounds confirmed the anisobidentate pattern of the {(RnECS2}− (E = O, n = 1; E = N, n = 2) monoanionic ligand. The presence of halides and sulfur atoms enhanced the formation of CH⋯X, S⋯H, S⋯S, and pi⋯H non-covalent interactions in the crystalline state. A Hirshfeld surface analysis was carried out to identify these significant intermolecular contacts in the complexes. The less hindered tin atom in the xanthate complexes displayed a CS⋯X–Sn interaction of attractive nature.