Abstract. fi-Na2UF6, hexagonal, P3, a = 6.112 (2), c = 7.240 (2) A, Z --2. Intensities were measured diffractometrically. There are two uranium ions in the asymmetric unit and each of these ions has nine nearest-neighbour fluorine ions at the corners of capped trigonal prisms. The U-F distances range from 2.23 (1) to 2.42 (1) A. There are four independent Na ions. Two are in the same type of crystallographic site and are also in the same type of polyhedron as the uranium ions. The other two have six coordination. The Na-F distances range from 2.25 (2) to 2.73 (2) A.
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