Na3MnO3 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted corner-sharing NaO4 tetrahedra. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1) and three equivalent O(2) atoms. Mn(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded to one Na(1), three equivalent Na(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing ONa4Mn trigonal bipyramids.
Na3MnO3 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted corner-sharing NaO4 tetrahedra. Both Na(1)-O(1) bond lengths are 2.36 Å. Both Na(1)-O(2) bond lengths are 2.30 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1) and three equivalent O(2) atoms. The Na(2)-O(1) bond length is 2.65 Å. There is one shorter (2.25 Å) and two longer (2.33 Å) Na(2)-O(2) bond lengths. Mn(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Mn(1)-O(1) bond lengths are 1.98 Å. Both Mn(1)-O(2) bond lengths are 1.89 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded to one Na(1), three equivalent Na(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing ONa4Mn trigonal bipyramids.