Ca₄Au₁₀In₃: Synthesis, Structure, and Bonding Analysis. The Chemical and Electronic Transformations from the Isotypic Zr₇Ni₁₀ Intermetallic

Abstract

The title compound, Ca(4)Au(10)In(3) (e/a = 1.59), was synthesized by conventional high-temperature solid-state reactions and structurally analyzed by single-crystal X-ray diffraction: space group Cmca, a = 13.729(4) A, b = 10.050(3) A, c = 10.160(3) A, Z = 4. The structure, isotypic with that of Zr(7)Ni(10), features a novel three-dimensional [Au(10)In(3)] polyanionic framework built from sinusoidal Au layers that are interconnected by significant Au-Au and Au-In interactions. A prominent electronic feature is the presence of a pseudogap and empty bonding states above the Fermi level according to LMTO calculations, reminiscent of the tunable electronic properties discovered for Mg(2)Zn(11)-type phases. The natures of the chemical and electronic redistributions from Zr(7)Ni(10) to Ca(4)Au(10)In(3) are considered. The Au backbone appears to be particularly important.