Y[PS4]: An Unusual ABX4 Compound with a PtS-Related Crystal Structure

Pale yellow single crystals of YPS₄] (tetragonal, I4₁/acd; a = 1065.72(5), c = 1899.23(9) pm, Z = 16) can easily be obtained by the reaction of the elements without using a flux to avoid the entrapment of alkali metals. The structure consists of isolated PS₄]^3- tetrahedra (d(P-S) = 203 pm, 4×) each surrounded by four Y³⁺ cations resulting in a S₄N₄-analogous arrangement of the metal cations and sulfur atoms about the phosphorus in the center of this polyhedron. Both crystallographically different Y³⁺ cations are eightfold coordinated by sulfur in the shape of trigonal dodecahedra (d(Y-S) = 280 - 300 pm, CN = 8) which in turn belong to four exclusively edge-attached PS₄]^3- tetrahedra. These build up a distorted cubic closest packing where the Y³⁺ cations are situated in one half of the tetrahedral holes the same way as S^2- in the Pt²⁺ arrangement of the PtS-type structure.