Abstract Three new organotin(IV) structures of general formula RSn(S 2CN R′ R″) 2Cl, where R′ ≠ R″, namely MeSn · [S 2CN(Me)(Cy)] 2Cl ( 1), MeSn[S 2CN( i-Pr)(CH 2Ph)] 2Cl ( 2) and PhSn[S 2CN(Et)( i-Pr)] 2Cl ( 3) are described. Each structure features tin in a distorted octahedral geometry defined by a C ClS 4donor set as a result of two chelating dithiocarbamate ligands. In all cases the tin-bound carbon and chloride atoms are cis. The shorter Sn–S bond lengths in 3are correlated with the presence of the relatively more electronegative Sn-bound phenyl substituent. The new structures conform to the structural motif adopted by all other compounds with the formula RSn(S 2CN R′ R″) 2Cl, where R′ = R″, suggesting the unsymmetrical substitution pattern of the dithiocarbamate ligands in the present study does not influence the adoption of this structural motif. The homogeneity in the structural motif notwithstanding, non-systematic variations in geometric parameters are found in these structures indicating an overall influence of crystal packing upon molecular geometry.