Different cation arrangements in Au-In networks. Syntheses and structures of six intermetallic compounds in alkali-metal-Au-In systems.

Six robust intermetallic compounds with cations in three different tunnel-like structures have been synthesized in alkali-metal-Au-In systems via high-temperature solid-state methods and characterized by X-ray diffraction: AAu(4)In(6) [A = K (I), Rb (II), P6m(2), Z = 1], K(1.76(6))Au(6)In(4) (III, I4/mcm, Z = 4), and A(x)Au(2)In(2) [x approximately 0.7, A = K (IV), Rb (V), Cs (VI), P4(2)/nmc, Z = 8]. The first type is constructed from a single cage unit: an alkali-metal-centered 21-vertex polyhedron A@Au(9)In(12) with 6-9-6 arrangement of planar rings. The others contain uniaxial arrays of tunnels built of differently puckered eight- and four-member Au/In rings. The largely different cation distributions depend on the tunnel constitutions and cation sizes. Tight-binding electronic structure calculations by linear muffin-tin-orbital (LMTO) methods were performed for I and idealized III in order to help understand their chemical bonding. These also reveal large differences in relativistic effects for Au d orbitals, as well as for different Au sites in each structure.