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

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 Csingle bondH?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 Cdouble bondS?X?Sn interaction of attractive nature.