A series of tin(IV) derivatives of 1,6-bis(pyrimidin-2-ylthio)hexane (pth) have been investigated by Mössbauer spectroscopy to elucidate aspects concerning structure and bonding in solid state. The SnClPh₃ (1) and SnCl₂Ph₂ (2) derivatives have 5- and 6-coordinate metal centres respectively. The phenyl groups of the diphenyltin(IV) derivative are in cis configuration as revealed by its isomer shift and quadrupole splitting as well as by the estimated C-Sn-C bond angle. The spectrum of the SnCl₃Ph (3) derivative reveals three phases in solid state as a mixture of chemicals having tetrahedral and octahedral geometries. The magnitude of both isomer shift and quadrupole splitting of SnCl₃Ph (3a) is smaller than the other two sites (3b and 3c) as a result of dephenylation of the metal precursor. The SnCl₄ (4) derivative has an octahedral geometry with the ligand bonded through the pyrimidyl moiety of pth. This polydentate compound is a weak σ-donor, in comparison to pyrazin, and it is acting as a bridging-bidentate as well as bridging-tetradentate ligand upon coordination. The ρ value (QS/IS ratio) of all organotin(IV) derivatives supports coordination number higher than four, except the compound from the 3c site.