Synthesis and structure of new two‐dimensional group 4 metal palladium sulfides, A2MPd3S6 (A = Rb, M = Hf; A = Cs, M = Zr, Hf)

Abstract

AbstractA series of new quaternary group 4 metal palladium sulfides, A2MPd3S6 (A = Rb, M = Hf; A = Cs, M = Zr, Hf) have been prepared from elements with the use of alkali metal halide fluxes and they are structurally characterized by single crystal x‐ray diffraction methods. They are isostructural and the structure of the title compounds consists of anionic [MPd3S62−] slabs and alkali metal ions. In the slab, the group 4 metals are surrounded by six S atoms in a trigonal prismatic fashion and the Pd atoms are coordinated with four S atoms in square planar fashion. Two hexagons made of six edge‐sharing square planar PdS4 are interconnected by two trigonal prismatic MS6 to form the basic repeating unit, M2Pd12S28. These are linked together to form the infinite two‐dimensional [MPd3S62−] slabs. These slabs stack on top of each other and they are separated by alkali metal cations. There is no strong SS bonding interaction in this phase and the charge valence of the title compounds could be expressed as [A+]2[M4+][Pd2+]3[S2−]6 (A = Rb, M = Hf; A = Cs, M = Zr, Hf).