The metal-rich antimonideZr2V6Sb9 has been prepared by arc-melting of stoichiometric mixtures of Zr, V, and VSb2. Zr2V6Sb9 is the first example of a ternary ordered (filled) variant of the unusual V15Sb18 structure type. In addition to strong metal–antimony bonding, the crystal structure is significantly stabilized by bonding V–V and Sb–Sb interactions, whereas the Zr atoms do not form short metal–metal
A synthetic and structural study of the zirconium-antimony system
作者:Eduardo Garcia、John D. Corbett
DOI:10.1016/0022-4596(88)90130-2
日期:1988.4
Ten phases have been obtained in the ZrSb system using arc-melting, annealing, powder sintering, vapor-phase transport, vaporization, and metal flux methods. In addition to the previous reported compositions (and structure types) Zr3Sb (Ni3P), Zr5Sb3 (Mn5Si3), and ZrSb2 (ZrSb2), there also exist Zr2Sb (La2Sb), high temperature Zr5Sb3 (Y5Bi3), ZrSb1−x (FeSi), ZrSb (ZrSb-Cmcm), and low temperature ZrSb2−x
The antimonides ZrNiSb and HfNiSb were prepared by are-melting of stoichiometric mixtures of Zr, ZrSb2 and Ni, and Hf, HfSb2 and Ni, respectively. Unlike ZrCoSb and HfCoSb, which form the LiAlSi structure type, ZrNiSb and HfNiSb crystallize in the TiNiSi type. The lattice dimensions are a = 672.7(2) gm, b = 416.43(8) pm, c = 753.8(1) pm, V = 211.16(7)x10(6) pm(3) for ZrNiSb and a=662.3(5) pm, b = 413.3(3) pm, c = 746.8(8) pm, V=203.4(3)x10(6) pm(3) for HfNiSb (space group Pnma). Whereas no Zr-Zr contacts <400 pm occur in the structure of ZrCoSb, Zr-Zr bonds are found in the structure of ZrNiSb. This difference is a consequence of the different numbers of valence electrons. The structural differences come along with a drastic change in the electronic structure and in the physical properties: ZrNiSb exhibits metallic behavior, in contrast to the not conducting ZrCoSb.
Haase, Martin G.; Block, Helga; Jeitschko, Wolfgang, Zeitschrift für anorganische und allgemeine Chemie
作者:Haase, Martin G.、Block, Helga、Jeitschko, Wolfgang