Zr6STe2 – ein zirconiumreiches Sulfidtellurid mit einer Zr3Te‐Teilstruktur vom Re3B‐Typ

Zr₆STe₂ – a Zirconium‐rich Sulfide Telluride with a Zr₃Te Partial Structure of the Re₃B Type Zr₆STe₂ is accessible through the reduction of a mixture of ZrTe₂ and ZrS₂ with zirconium in fused tantalum tubes at 1520 K. The spatially averaged crystal structure of Zr₆STe₂ is described in the space group Cmcm, a = 377.81(4), b = 1156.4(1), c = 887.96(8), Z = 2, Pearson symbol oC18, 320 reflexions (I > 2σ(I)), 22 variables, R_w(I) = 0.088. Zr₆STe₂ crystallizes in a unique structure type, which can be seen as a filled Re₃B type structure. The tellurium atoms are surrounded by nine zirconium atoms situated at the vertices of a distorted, tricapped trigonal prism. The Zr₉Te tetrakaidecahedra are connected by common triangular prism faces parallel 100], edges approximately along 001] and common vertices along 010], thus forming a three‐dimensional tetrakaidecahedral network Zr_9/3Te], which is decisively stabilized by homonuclear Zr–Zr‐interactions. The tetrakaidecahedra are arranged in such a way, that Zr₆ octahedra occur. The octahedra are arranged into layers by sharing edges parallel 100] and vertices along 001]. As a result of a distortion of the structure, every second octahedron is expanded to such an extent as to be able to smoothly accommodate sulfur atoms. According to the modulation of the diffraction intensities, the vacancy ordering in adjacent layers of octahedra occurs independently of each other.