Tetranuclear heteroleptic mercury(ii) complexes of the composition [Hg4(S2CNPr2)6(NO3)2] and [Hg4(S2CNPr2)4Cl4]: structural organization, principles of construction of supramolecular polymeric chains, and thermal behavior

Abstract

New heteroleptic mercury(ii) complexes [Hg₄(S₂CNPr₂)₆(NO₃)₂] (1) and [Hg₄(S₂CNPr₂)₄Cl₄] (2) were synthesized and characterized by single-crystal X-ray dif raction and ¹³C and ¹⁵N MAS NMR spectroscopy. In these complexes, the metal atoms are linked in pairs by bridging dipropyldithiocarbamate ligands (Pr₂Dtc) to form tetranuclear cations and molecules. The further structural organization of compound 1 to the polymeric chains [Hg₄(S₂CNPr₂)₆(NO₃)₂]_n occurs due to the linking of [Hg₄(S₂CNPr₂)₆]²⁺ cations by pairs of bridging nitrate groups. The formation of the supramolecular polymeric structure of 2 is determined by pairwise secondary Hg⋯Cl bonds between the cyclic [Hg₄(S₂CNPr₂)₄Cl₄] molecules, in which the central eight-membered metallocycle [Hg₄S₄] adopts a distorted chair conformation. The thermal behavior of compounds 1 and 2 was studied by simultaneous thermal analysis.