Synthesis and crystal structure of two synthetic oxofluoride framework compounds – Co2TeO3F2 and Co2SeO3F2

Abstract

Two new isostructural Co²⁺ containing tellurium and selenium oxofluoride compounds Co₂TeO₃F₂ and Co₂SeO₃F₂ are synthesized and their structures determined by single crystal X-ray diffraction. They crystallize in the orthorhombic space group Pnma with the unit cell parameters a = 7.3810(5) Å, b = 10.1936(7) Å, c = 5.3013(3) Å and a = 7.2655(8) Å, b = 10.0013(13) Å, c = 5.3564(6) Å, respectively. The Co(II) ion has octahedral coordination [CoO₃F₃] and builds up a 3D framework by corner- and edge sharing. The Se(IV) and the Te(IV) ions have the coordinations [SeO₃E] and [TeO₃E] respectively where E is the lone-pair electrons. The Se(IV) and Te(IV) ions are isolated from each other and bond only to the [CoO₃F₃] polyhedra. The electronegative element fluorine takes the role of a network builder like oxygen and helps to form the 3D framework structure. This is a difference compared to many oxohalide compounds containing Cl and Br where the halide ions are terminating ions preventing a 3D network from being formed. Long range antiferromagnetic interactions dominate at temperatures < 20 K. The magnetic susceptibility follows the Curie–Weiss law above 25 K with the Curie constant C = 5.62 emu K mol⁻¹, the Weiss temperature θ = −56 K and the effective magnetic moment μ_eff = 4.74 μ_B per cobalt atom.