Four new bis(dialkyldithiocarbamates) of zinc, [Zn(S 2 CNMeR) 2 ] 2 (where R = Et, Pr n , Pr i and Bu n : compounds 1, 2, 3 and 4 have been synthesized and characterized by X-ray crystallography, spectroscopic methods and differential scanning calorimetry. X-ray crystallographic characterization indicated centrosymmetric dimeric structures for 1-4. The central region of each molecule, consisting of three edge-sharing four-membered rings, is structurally similar to the symmetric bis(dialkyldithiocarbamates) [Zn(S 2 CNEt 2 ) 2 ] 2 and [Zn(S 2 CNPr i 2 ) 2 ] 2 , characterized in earlier studies. Preliminary results on chemical vapour deposition of polycrystalline ZnS films from 4, which is considerably more volatile than the previously used precursor [Zn(S 2 CNEt 2 ) 2 ] 2 , are reported.