Neutron diffraction studies of U4O9: comparison with EXAFS results.

Conradson et al. have analyzed X-ray absorption fine-structure spectra of the UO2-U4O9 system and concluded that oxygen atoms are incorporated in U4O9 as oxo groups with U-O distances in the range 1.72-1.76 A. They also found that the uranium sublattice consists of an ordered portion and an additional 'spectroscopically silent' glassy portion. We have carried out studies of powdered U4O9 by neutron diffraction which contradict these conclusions from EXAFS measurements. Our analysis shows that there are no U-O bonds shorter than 2.2 A and that U4O9 is crystallographically ordered with no evidence of a glassy structure.

U4O9: atoms in general sites giving the hkl extinctions of special sites.

In U4O9, most of the atoms are in general 48-fold [48(e)] sites of the space group I43d and yet the hkl reflections obey the extinction rules for atoms occupying special 12-fold [12(b)] sites. An explanation is given for this effect, which can be generalized to any space group.

Refinement of the structure of beta-U4O9.

Beta-U4O9 is a superlattice structure based on the fluorite arrangement of UO2. The U atoms occupy positions close to those in UO2 and the additional O atoms are accommodated in cuboctahedral clusters of 43m symmetry, which are centred on the special 12-fold sites of the cubic space group I43d. The structure has been refined from single-crystal neutron data in accordance with the procedure described in the previous paper [Popa & Willis (2004). Acta Cryst. A60, 318-321].