The structural chemistry of organotin derivatives of 5-mercapto-3-phenyl-1,3,4-thiadiazoline-2-thione: supramolecular structures involving intermolecular Sn⋯S, N–H⋯S or S⋯S interactions

Abstract

Seven new organotin complexes of 5-mercapto-3-phenyl-1,3,4-thiadiazoline-2-thione (I), R_nSn(PhN₂C₂S₃)_{4 − n} [n = 1, R = Bu (1); n = 2, R = Ph (2), Bu (3), Me (4) and n = 3, R = Ph (5), Bu (6), Me (7)], along with the 4,4′-bipy and 4-PyNH₂ adducts of 7, [Me₃Sn(PhN₂C₂S₃)]₂·(4,4′-bipy) (8) and [Me₃Sn(4-PyNH₂)₂]⁺[PhN₂C₂S₃]⁻ (9), respectively, have been synthesised. The coordination behaviour of I in 1–8 ranges from S(1) monodentate to S(1) + S(3) bidentate bridging, while the crystal structure of 9 contains the ligand as a non-bonded anion. The supramolecular structures of 2, 7 and 8 have been found to consist of 1-D molecular chains built up by Sn⋯S (7) or S⋯S (2, 8) intermolecular linkages. Additionally, the 1-D polymers of 7 aggregate in ‘ribbon’-type double chains through S⋯S interactions and further self-organise via Ph⋯Ph face-to-face π-stacking, leading to a 3-D network. Extended intermolecular N–H⋯S interactions in the crystal lattice of 9 link the molecules in a 3-D network.