Na2UO4 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 7-coordinate geometry to three equivalent O(2) and four equivalent O(1) atoms. U(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing UO6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one U(1) atom. In the second O site, O(2) is bonded to three equivalent Na(1) and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ONa3U2 trigonal bipyramids.
Na2UO4 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 7-coordinate geometry to three equivalent O(2) and four equivalent O(1) atoms. There are a spread of Na(1)-O(2) bond distances ranging from 2.33-2.68 Å. There are two shorter (2.42 Å) and two longer (2.48 Å) Na(1)-O(1) bond lengths. U(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing UO6 octahedra. Both U(1)-O(1) bond lengths are 1.93 Å. All U(1)-O(2) bond lengths are 2.18 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to four equivalent Na(1) and one U(1) atom. In the second O site, O(2) is bonded to three equivalent Na(1) and two equivalent U(1) atoms to form a mixture of edge and corner-sharing ONa3U2 trigonal bipyramids.