The N(4)-methylthiosemicarbazone derivatives H2DDMT (1) and H2DMMT (2) have been prepared from the reaction of 4-methylthiosemicarbazide with 2,3-dihydroxybenzaldehyde and 2-hydroxy-5-methylbenzaldehyde, respectively. Six new organotin(IV) complexes, [MeSnCl(DDMT)] (3), [BuSnCl(DDMT)] (4), [PhSnCl(DDMT)] (5), [MeSnCl(DMMT)] (6), [BuSnCl(DMMT)] (7), and [PhSnCl(DMMT)] (8) have been synthesized by direct reaction of corresponding organotin(IV) chloride(s) with these ligands. The ligands and their compounds have been characterized by elemental analysis, molar conductivity, UV–Vis, FT-IR, and NMR (1H, 13C, and 119Sn) spectroscopy. The molecular structures of 1 and 2 were determined by X-ray crystallography. Spectroscopic data suggested that the ligands were coordinated to tin(IV) as dinegative tridentate via phenoxide-O, azomethine-N, and thiolate-S atoms. The crystal structures revealed that the ligands exist in thione form in the solid state. In vitro cytotoxicity assays were carried out for all the compounds against MCF-7 cancer cell line. The results have shown that different organotin(IV) groups showed characteristic differences in their biological activity. Graphical abstract Six new organotin(IV) complexes with 2,3-dihydroxybenzaldehyde-N(4)-methylthiosemicarbazone H2DDMT (1) and 2-hydroxy-5-methylbenzaldehyde-N(4)-methylthiosemicarbazone H2DMMT (2), [MeSnCl(DDMT)] (3), [BuSnCl(DDMT)] (4), [PhSnCl(DDMT)] (5), [[MeSnCl(DMMT)] (6), [BuSnCl(DMMT)] (7), and [PhSnCl(DMMT)] (8) have been synthesized. The ligands are coordinated to tin(IV) through the phenoxide-O, azomethine-N, and thiolate-S as a dinegative tridentate chelating agent; the coordination number of tin is five. In vitro cytotoxicity assays against MCF-7 cancer cell line showed that 3–8 possess activity.