The Tetrachloridoaurates(III) of Zinc(II) and Cadmium(II)

The first salt‐like compounds of dications with [AuCl 4 ] – anions are reported. The compounds Zn[AuCl 4 ] 2 · (AuCl 3 ) 1.115 ( 1 ) and Cd[AuCl 4 ] 2 ( 2 ) are obtained from reactions of M Cl 2 ( 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 C 2/ c ( α 0 γ )0 s ] 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[AuCl 4 ] 1/1 [AuCl 4 ] 2/2 }. The second subsystem consists of Au 2 Cl 6 molecules, which are located in channels built up by the first subsystem. The structural parameters of the hosted Au 2 Cl 6 molecules show only small deviations from neat AuCl 3 . The crystal structure of Cd[AuCl 4 ] 2 ( 2 ) consists of chains built of Cd 2+ ions coordinated by bridging [AuCl 4 ] – anions and alternating Cd‐Au sequence. Cd has a distorted octahedral coordination environment.