RESUMEN
The single-crystal diffraction study of Ce10W22O81 and powder X-ray diffraction (XRD) experiments on Ce10W22O81 and Nd10W22O81 show that the true space group of these phases is Pbnm, contrary to the previous literature reports of the space groups Pbcn and Pbcm for the rare-earth tungstates (RE = La, Ce, Pr, Nd) with this general formula. The structure contains rare-earth cations in seven-, eight- and ninefold coordination. W atoms are found in corner-sharing WO5 groups, and also in WO6 and WO7 polyhedra which share edges and corners to form W6O17 units. The new model obtained from our single-crystal work gives better agreement with powder XRD data on both Ce10W22O81 and Nd10W22O81, and gives more plausible coordination environments and bond-valence sums.