Na2UO4 crystallizes in the orthorhombic Pccn space group. Na(1) is bonded in a 5-coordinate geometry to two equivalent O(1) and three equivalent O(2) atoms. U(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing UO6 octahedra. The corner-sharing octahedral tilt angles are 32°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent U(1) atoms to form a mixture of distorted edge and corner-sharing ONa2U2 trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one U(1) atom.
Na2UO4 crystallizes in the orthorhombic Pccn space group. Na(1) is bonded in a 5-coordinate geometry to two equivalent O(1) and three equivalent O(2) atoms. There is one shorter (2.43 Å) and one longer (2.64 Å) Na(1)-O(1) bond length. There are a spread of Na(1)-O(2) bond distances ranging from 2.33-2.66 Å. U(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing UO6 octahedra. The corner-sharing octahedral tilt angles are 32°. Both U(1)-O(2) bond lengths are 1.94 Å. There are two shorter (2.17 Å) and two longer (2.21 Å) U(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent U(1) atoms to form a mixture of distorted edge and corner-sharing ONa2U2 trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one U(1) atom.