Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Double Three-Dimensional Pseudo-Polymer Complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] Comprising the New Type Silver(I) Anion

New crystalline pseudo-polymer complex [Au{S2CN(CH2)(6)}(2)](4)[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S2CN(CH2)(6)}(2)](+) (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9](4-) are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl<middle dot><middle dot><middle dot>S and Ag<middle dot><middle dot><middle dot>S, hydrogen bonds C-H<middle dot><middle dot><middle dot>Cl, and anagostic interactions C-H<middle dot><middle dot><middle dot>Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)-Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.