A series of tri-, chlorodi-, and diorganotin(IV) derivatives of 4-(2-methoxyphenyl)piperazine-1-carbodithioate (L) {R ¼ n-C 4 H 9 (1), C 6 H 11 (2), CH 3 (3) and C 6 H 5 (4)}, (n-C 4 H 9 ) 2 SnClL (5) and R 2 SnL 2 {R ¼ n-C 4 H 9 (6), C 2 H 5 (7), CH 3 (8)} have been synthesized by refluxing organotin(IV) chlorides with the ligand-salt in the appropriate molar ratio. Elemental analysis, Raman, IR, multinuclear NMR ( 1 H, 13 C and 119 Sn), mass spectroscopic, and single-crystal X-ray crystallographic studies were undertaken to elucidate the structures of the new compounds both in solution and in the solid state. The X-ray diffraction work reveals supramolecular structures for 4 and 6, with distorted trigonal-bipyramidal and distorted octahedral geometries around Sn, respectively. The ligand and several of the new compounds are good antimicrobial agents.