Structures and properties of NbOF3 and TaOF3 - with a remark to the O/F ordering in the SnF4 type structure

Abstract

Powder samples of NbOF3 und TaOF3 were prepared by heating mixtures of NbO2F and NbF5 or TaO2F and TaF5, respectively, in the corresponding stoichiometric ratio in platinum crucibles under argon atmosphere (180-220degreesC). Both oxide fluorides are coulourless with a slight greyish tinge. They are sensitive to moisture and decompose in air at room temperature within hours. Both, NbOF3 and TaOF3 crystallize as a variant of the SnF4 type structure, space group 14/mmm. The structures have been refined from X-ray powder diffraction data using the Rietveld method (a = 3.9675(1) Angstrom, c = 8.4033(1) Angstrom, R-B = 3.60%, R-p = 4.58% for NbOF3 and a = 3.9448(1) Angstrom, c = 8.4860(1) Angstrom, R-a = 2.07%, R-p = 2.44% for TaOF3). Characteristic building units are sheets of corner sharing MX6 octahedra which are stacked via van der Waals interactions to a three dimensional framework. The occupancy of the two crystallographic sites for the anions by O and F is discussed on the basis of structure refinements, bond order summations, IR and NMR data and calculations of the Madelung parts of the lattice energy.