Multiple Isomerization of Structural Units in Ion-Polymeric Heteronuclear Gold(III)-Zinc(II) Complex ([Au{S2CN(C4H9)(2)}(2)](2)[ZnCl4])(n): Chemisorption-Based Synthesis, Supramolecular Structure (Self-Organization of Long-Period Cation-Cationic Polymer Chains), and Thermal Behavior

摘要

Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc dithiocarbamate [Zn-2{S2CN(C4H9)(2)}(4)] resulted in the formation of a polymeric heteronuclear gold(III)-zinc(II) dithiocarbamato-chlorido complex ([Au{S2CN(C4H9)(2)}(2)](2)[ZnCl4])(n) (I), which was characterized by MAS C-13 NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Compound I isolated on a preparative scale was found to have a highly intricate supramolecular structure composed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S2CN(C4H9)(2)}(2)](+), with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl4](2-) anions. The isomeric gold(III) cations perform different structural functions. Four and six cations are involved in the formation of two sorts of long-period cation-cationic chains (via pair non-valence secondary Au center dot center dot center dot S bonds): (center dot center dot center dot A center dot center dot center dot B center dot center dot center dot C center dot center dot center dot D center dot center dot center dot C center dot center dot center dot B center dot center dot center dot)(n) and (center dot center dot center dot F center dot center dot center dot G center dot center dot center dot H center dot center dot center dot I center dot center dot center dot J center dot center dot center dot K center dot center dot center dot)(n) . The discrete E, L, and M cations and the [ZnCl4](2-) complex anions are located alongside of the polymer chains and do not take part in the secondary interactions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarbamate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial conversion to ZnS in the anion.