Abstract
A family of quaternary (or pseudoquaternary) antimonides Nb4Pd0.5ZSb2 (Z = Cr, Fe, Co, Ni, Si) containing up to three transition metals in an ordered arrangement has been prepared by reactions of the elements. These antimonides are isostructural, crystallizing as substitutional variants of the W5Si3-type structure (tetragonal, space group -I4/mcm, Z = 4) with unit cell parameters a = 10.4407(3) A and c = 5.0020(2) A for Nb4Pd0.5Cr0.28(3)Si0.72Sb2, a = 10.4825(6) A and c = 4.9543(3) A for Nb4Pd0.5FeSb2, a = 10.4603(5) A and c = 4.9457(3) A for Nb4Pd0.5CoSb2, a = 10.4332(7) A and c = 4.9649(3) A for Nb4Pd0.5Ni0.78(1)Sb2, and a = 10.3895(10) A and c = 4.9634(4) A for Nb4Pd0.5SiSb2. They are distinguished by the filling of interstitial Z atoms into the centers of Nb8 square antiprismatic clusters that are linked by PdSb4 tetrahedra. The Nb8 square antiprisms share opposite square faces to form one-dimensional chains along the c axis so that Z-Z bonding distances of approximately 2.5 A result. Extended Hückel band structure calculations were carried out to interpret the homo- and heteroatomic metal-metal interactions in the structure. The resistivity of one member, Nb4Pd0.5SiSb2, was measured, indicating metallic behavior.
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