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

Seven new organotin complexes of 5-mercapto-3-phenyl-1,3,4-thiadiazoline-2-thione (I), RnSn( 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 pi-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.