| Abstract: | The first salt‐like compounds of dications with [AuCl4]– anions are reported. The compounds Zn[AuCl4]2 · (AuCl3)1.115 ( 1 ) and Cd[AuCl4]2 ( 2 ) are obtained from reactions of MCl2 (M = Zn, Cd) and elemental gold in liquid chlorine at ambient temperature under autogenous pressure and subsequent annealing at 230 °C. The structure of 1 represents an incommensurately modulated composite [superspace group C2/c(α0γ)0s] built of two subsystems. The first subsystem contains chains of zinc(II) tetrachloridoaurate(III), which feature a slightly distorted octahedral coordination of Zn and can be described by the Niggli formula 1∞{Zn[AuCl4]1/1[AuCl4]2/2}. The second subsystem consists of Au2Cl6 molecules, which are located in channels built up by the first subsystem. The structural parameters of the hosted Au2Cl6 molecules show only small deviations from neat AuCl3. The crystal structure of Cd[AuCl4]2 ( 2 ) consists of chains built of Cd2+ ions coordinated by bridging [AuCl4]– anions and alternating Cd‐Au sequence. Cd has a distorted octahedral coordination environment. |
