Abstract
Rb4PbBr6 was prepared by solid state reaction of the binary compounds and the structure refined with single crystal data (a = 1332.9(4), c = 1647.8(5) pm; space group R3c; K4CdCl6‐type arrangement). Attempts to synthesize Rb4HgI6 and K4CdI6 were unsuccessful. The results are discussed on the basis of a structure field diagram for A4BX6 compounds.