NaMo4O6 crystallizes in the tetragonal P4/mbm space group. Na(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 7-coordinate geometry to three equivalent O(2) and four equivalent O(1) atoms. In the second Mo site, Mo(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 2-37°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Mo(1), and two equivalent Mo(2) atoms to form a mixture of distorted corner, face, and edge-sharing ONa2Mo4 octahedra. The corner-sharing octahedral tilt angles range from 0-77°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Mo(2) and three equivalent Mo(1) atoms.
NaMo4O6 crystallizes in the tetragonal P4/mbm space group. Na(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. All Na(1)-O(1) bond lengths are 2.97 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 7-coordinate geometry to three equivalent O(2) and four equivalent O(1) atoms. There are two shorter (2.49 Å) and one longer (2.80 Å) Mo(1)-O(2) bond length. All Mo(1)-O(1) bond lengths are 2.33 Å. In the second Mo site, Mo(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 2-37°. Both Mo(2)-O(2) bond lengths are 2.01 Å. There are two shorter (2.19 Å) and two longer (2.28 Å) Mo(2)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Mo(1), and two equivalent Mo(2) atoms to form a mixture of distorted corner, face, and edge-sharing ONa2Mo4 octahedra. The corner-sharing octahedral tilt angles range from 0-77°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Mo(2) and three equivalent Mo(1) atoms.