A series of organotin(IV) derivatives of bis(pyrimidin-2-ylthio)methane ( ptm ), 1,2-bis(pyrimidin-2-ylthio)ethane ( pte ) and 1,6-bis(pyrimidin-2-ylthio)hexane ( pth ) have been prepared in dichloromethane at room temperature. The 2:1 (M/L) molar ratio compounds have a general formula of [Sn 2 Cl x Ph 8-x L] ( x = 2, 4, 6, 8; L = ptm , pte and pth ). A 1:1 complex was also obtained by reacting SnClPh 3 with pth . The organotin derivatives were characterised by multinuclear NMR ( 1 H, 13 C and 119 Sn) and infrared spectroscopy, gel permeation chromatography (GPC), microanalysis and melting point. In the triphenyltin derivatives, 1 , 5 , 9 and 10 the tin atoms show a distorted trigonal-bipyramidal confi guration where the ligand is monodentate towards the metal atom. In the compounds 2 -4 , 6 -8 and 11 -13 , the tin atoms each exhibit a distorted octahedral confi guration. Chelation is formed between the tin nucleus and the coordinating sulphur and nitrogen atoms. The correlation between the 1 J ( 13 C-119 Sn) and C-Sn-C bond angle indicates formation of 5-coordinate compounds.