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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 μeff = 4.74 μB per cobalt atom.
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