Some new tri-, chlorodi- and diorganotin(IV) dithiocarboxylates (1-10) of 4-benzylpiperidine-1-carbodithioate ligand (L), with general formulae R3SnL {R = n-C4H9 (1), C6H11 (2), CH3 (3) and C6H5 (4)}, R2SnClL {R = n-C4H9 (5), C2H5 (7), CH3 (9)} and R2SnL2 {R = n-C4H9 (6), C2H5 (8), CH3 (10)}, have been synthesized by the reaction of organotin(IV) chlorides with the ligand-salt in the appropriate molar ratio. Elemental analysis, Raman, IR, multinuclear NMR (H-1, C-13 and Sn-119) and X-ray crystallographic studies have been undertaken to elucidate the structures of the complexes, both in solution and in solid state. Single-crystal X-ray diffraction study indicate trimeric, dimeric, supramolecular cyclic and supramolecular zig-zag chain structures for complexes 2, 4, 6 and 9, respectively. Square-pyramidal geometry is attributed to complex 9 on the basis of the tau value (0.4). A subsequent antimicrobial study indicates that the compounds are biologically active. (c) 2009 Elsevier Ltd. All rights reserved.