High-quality X-ray data on the emerald green crystals were first refined to an R factor of 0.027 in terms of an octahedral trans,trans,trans-ReO2Cl2(PPh(3))(2) molecule sitting on a crystallographic inversion center. No anomalies were detected in thermal ellipsoids, bond lengths, and electron density maps. In conjunction with spectroscopic and magnetic data, the crystal was eventually found to contain trans,trans,trans-ReOFCl2(PPh(3))(2) molecules disordered over two orientations. The structure at left illustrates the limitations of X-ray crystallography at detecting orientational disorder involving atoms of similar atomic numbers.