Syntheses and Crystal Structures of Diorganotin Derivatives of 2,5‐Dimercapto‐1,3,4‐thiadiazole

Two novel trinuclear tin oxo clusters [(C 2 S 3 N 2 )R 6 Sn 3 O(OH)Y]·L [R = CH 3 , Y = OH, L = 1·5H 2 O ( 1 ); R = PhCH 2 , Y = OEt, L = 0 ( 2 )], a pentanuclear tin macrocycle [(CH 3 ) 2 Sn(C 2 N 2 S 3 )] 5 ·CH 2 Cl 2 ·3H 2 O ( 3 ) and [(PhCH 2 ) 4 Cl 2 Sn(C 2 S 3 N 2 )] ( 4 ) have been synthesized by the reaction of 2,5‐dimercapto‐1,3,4‐thiadiazole with dialkyltin dichloride in ethanol (95%) or dichloromethane. Complexes 1 − 4 have been characterized by elemental analysis and IR, 1 H, 13 C and 119 Sn NMR spectroscopy. The structures of 1 − 3 have been determined by X‐ray crystallography. Complexes 1 and 2 display a unique tricyclic structure consisting of fused five‐membered Sn 2 ON 2 and four‐membered Sn 2 O 2 rings that form a planar N 2 Sn 3 O 2 skeleton, with a distorted trigonal bipyramidal coordination at tin. Complex 3 is a pentanuclear 35‐membered tin macrocycle containing the crown thioether‐type ligand in which all five tin atoms bond to the sulfur and nitrogen atoms with distorted octahedral geometries. The structures of complexes 1 and 3 are stabilized by hydrogen bonds or intermolecular non‐bonding S ··· S interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)