Synthesis and structure of A4V6[Te24+Te6+]O24 (A = K, Rb)—two new quaternary mixed-valent tellurium oxides

Abstract

Two new mixed-valent tellurium oxides with vanadium(V), A(4)V(6)[Te(2)(4+)Te(6+)]O(24) (A = K and Rb), have been synthesized by hydrothermal and conventional solid state techniques. Their structures were determined by single-crystal X-ray diffraction analysis. These two iso-structural compounds exhibit layered structural topologies consisting of [V(6)Te(3)O(24)](4-) anionic units. In these anionic structural units, a Te(6+)O(6) octahedron is connected to six VO(4) tetrahedra by corner-sharing to generate a [V(6)TeO(24)] unit, and each of these [V(6)TeO(24)] units are interconnected by sharing two Te(4+)O(3) polyhedra to complete the infinite [V(6)Te(3)O(24)](4-) sheets. Infrared spectroscopy, UV-Visible diffuse reflectance spectroscopy, and thermogravimetric analysis were also performed on these two compounds. Crystal data: K(4)V(6)Te(3)O(24), trigonal, space group R ̅3c (No. 167) with a = b = 9.7075(6) Å, c = 42.701(3) Å, V = 3484.9(4) Å(3), and Z = 6; Rb(4)V(6)Te(3)O(24), trigonal, space group R ̅3c (No. 167) with a = b = 9.8399(9) Å, c = 43.012(4) Å, V = 3606.6(6) Å(3), and Z = 6.