Abstract
Zr 1− δ V 1+ δ As is accessible via arc-melting of different mixtures of ZrAs, VAs, Zr, and V. It crystallizes in the tetragonal La 2Sb type, with a phase range of −0.43(4)⩽ δ⩽0.15(1). The lattice dimensions ( a=382.4(1) pm, c=1486.8(6) pm for Zr 1.43(4)V 0.57As; and a=375.77(7) pm, c=1400.2(3) pm for Zr 0.85(1)V 1.15As) strongly depend on δ because of the different sizes of the Zr and V atoms. The ZrVAs structure comprises sheets of (empty) M 6 octahedra, whose triangular faces are capped by the main group atoms Q. The sheets are interconnected via M− Q bonds to a truly three-dimensional structure. Like in the isostructural ZrTiAs, the smaller 3 d M atom prefers the site in the densely packed square planes. In addition to the dominating M−As bonds, the structure comprises strong M− M bonding. Independent of the exact Zr:V ratio, Zr 1− δ V 1+ δ As is calculated to have three-dimensional metallic properties.
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