Two new crystalline dithiocarbamato-chlorido complexes of mercury(II), [Hg₂{S₂CN(C₄H₉)₂}₂Cl₂] (1) and [Hg₄{S₂CN(iso-C₄H₉)₂}₆][Hg₂Cl₆] (2), have been prepared and chemically identified by solution (¹H, ¹³C) NMR and solid-state (¹³C, ¹⁵N) CP-MAS NMR and FT-IR spectroscopy. The crystal, molecular and supramolecular structures of these compounds were established using single-crystal X-ray diffraction (XRD) analysis. The obtained complexes reveal two principally different types of structural organisation. In the structure of the former neutral complex, there are two isomeric doubly-bridged binuclear molecules [Hg₂(S₂CNBu₂)₂Cl₂] (‘A’ and ‘B’), whereas the latter compound comprises two ionic structural moieties: the tetranuclear cation [Hg₄(S₂CNⁱBu₂)₆]²⁺ and the binuclear anion [Hg₂Cl₆]²⁻. In both ionic units, pairs of ⁱBu₂Dtc or chloride ligands, which perform a bridging structural function, combine with neighbouring mercury atoms. In turn, intermolecular/interionic secondary interactions Hg···S/Hg···Cl are involved in the formation of supramolecular structures of complexes 1/2, yielding pseudo-polymeric chains of (···‘A’···‘B’···)n/(···[Hg₄(S₂CNⁱBu₂)₆]···[Hg₂Cl₆]···)n, which exhibit alternation of isomeric molecules of 1/ionic moieties of 2 along their lengths. Despite the significant structural difference between the above complexes, we established, using simultaneous thermal analysis (STA), that both exhibit very similar thermal behaviour. Moreover, during the thermal transformations of both compounds 1 and 2, the same two substances are generated: HgCl₂ and HgS.