Chlorometallates of transition and B subgroup elements are readily prepared and precipitated by reaction of the corresponding metallic salts with 1-methyl-4,4-dimercaptopiperidinium chloride. These chlorometallates investigated were [ZnCl4]2-, [CdCl3]-, [CoCl4]2-, [CuCl5]3- and [FeCl4]2-. Strong SH ... Cl interactions, but not NH ... Cl, have been evidenced by IR spectroscopy in the zinc, cadmium and cobalt complexes. The SH and NH absorptions are observed at ≅ 2480 cm-1 and 3060 cm-1, respectively. Partial deuteration of the [ZnCl4]2- complex with d1-methanol, shifted these IR signals to 1800 and 2260 cm-1, clearly evidencing a X-hydrogen type of bond. The SH ... Cl interaction is smaller in the [FeCl4]2- complex, and practically nonexistent in the [CuCl53- complex. © 1983.