Structural Variations across Wolframite Solid Solutions, (Fe,Mn)WO4

Abstract

The crystal structure of four samples from natural wolframite solid solutions, (Fe,Mn)WO4, was obtained with synchrotron high-resolution powder X-ray diffraction (HRPXRD) data, Rietveld refinements, space group P2/c, and Z = 2. Wolframite solid solutions extend from ferberite (FeWO4) to hübnerite (MnWO4). The W and (Mn,Fe) cations are in six-fold coordination. This study shows that the unit-cell parameters, a, b, c, and β angle, vary linearly with the unit-cell volume, V, across the wolframite series. The average <Mn,Fe–O> distance increases linearly because of larger Mn2+ (0.83 Å) replacing smaller Fe2+ (0.78 Å) cations, whereas the average <W–O> distance increases slightly because of the higher effective charge of the smaller Fe2+ cation. The distortions of the two types of polyhedra across the series are discussed.