Metal-rich polyantimonides: internal competition between M–M and Sb–Sb and heteroatomic M–Sb interactions in (Zr,V)₁₃Sb₁₀ and (Zr,V)₁₁Sb₈ (M = Zr,V)

Abstract

The title compounds are accessible by arc-melting of suitable mixtures of Zr, V and ZrSb₂. Their crystal structures were determined via single crystal measurements on an IPDS diffractometer. Depending on the M∶Sb ratio (M = Zr, V; M∶Sb = 13∶10 or 11∶8), the phases crystallize in two related structure types, namely Zr_7.5V_5.5Sb₁₀ and Cr₁₁Ge₈. The lattice dimensions of Zr_7.46(5)V_3.54Sb₈ are a = 1514.7(1), b = 570.77(5), c = 1811.1(2) pm, V = 1565.8(2) × 10⁶ pm³ (Pnma, Z = 4). The structures may be considered as intergrowths of (distorted) fragments of the W₅Si₃ and NiAs structure types. In addition to M–Sb and homonuclear (and heteronuclear) M–M bonds, Sb–Sb bonding interactions, with Sb–Sb distances shorter than in elemental antimony, occur in the linear Sb chains of the W₅Si₃-analogous structural motifs. The entropy-stabilized phases decompose by annealing at lower temperatures. The metallic character was confirmed via extended Hückel calculations as well as measurements of the electrical resistivities.

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