The formation and structural aspects of some metal complexes of thiosalicylic acid (TSA) were studied. The -bridging tetra-coordinated Ru complex, [Ru(C6H4(CO2)(mu-S)(H2O)](2) (1) was formed by hydrothermal reaction of TSA with RuCl3. The complexes [M(dtdb)(phen)(H2O)](n) (2-4) (M = Zn-II, Co-II, Ni-II, dtdb = 2,2-dithiodibenzoate anion, phen = 1,10-phenanthroline) were obtained by the slow diffusion technique and the in situ S-S bond formation was confirmed by elemental, spectral and X-ray analysis. Reaction of TSA with CuCl2 and 2,2'-bipyridine (bipy) under the slow diffusion technique yielded the dimer [Cu(tdb)(bipy)] (5) (tdb = thiodibenzoic acid), where the in situ generation of 2,2'-thiodibenzoic acid was observed.