Na4MnO3 crystallizes in the orthorhombic Ibca space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Na site, Na(2) is bonded to four equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Mn(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra,  an edgeedge with one Mn(1)O4 tetrahedra, edges with two equivalent Na(2)O4 tetrahedra, and edges with two equivalent Na(3)O4 tetrahedra. In the third Na site, Na(3) is bonded to four equivalent O(2) atoms to form NaO4 tetrahedra that share corners with four equivalent Na(2)O4 tetrahedra, corners with four equivalent Mn(1)O4 tetrahedra, edges with two equivalent Na(2)O4 tetrahedra, and edges with two equivalent Na(3)O4 tetrahedra. Mn(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form MnO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Mn(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra, and  an edgeedge with one Na(2)O4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to four equivalent Na(1) and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing ONa6Mn pentagonal bipyramids.
Na4MnO3 crystallizes in the orthorhombic Ibca space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. There is one shorter (2.28 Å) and one longer (2.61 Å) Na(1)-O(1) bond length. There is one shorter (2.28 Å) and one longer (2.47 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded to four equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Mn(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra,  an edgeedge with one Mn(1)O4 tetrahedra, edges with two equivalent Na(2)O4 tetrahedra, and edges with two equivalent Na(3)O4 tetrahedra. There are two shorter (2.41 Å) and two longer (2.45 Å) Na(2)-O(2) bond lengths. In the third Na site, Na(3) is bonded to four equivalent O(2) atoms to form NaO4 tetrahedra that share corners with four equivalent Na(2)O4 tetrahedra, corners with four equivalent Mn(1)O4 tetrahedra, edges with two equivalent Na(2)O4 tetrahedra, and edges with two equivalent Na(3)O4 tetrahedra. There are two shorter (2.28 Å) and two longer (2.37 Å) Na(3)-O(2) bond lengths. Mn(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form MnO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Mn(1)O4 tetrahedra, corners with four equivalent Na(3)O4 tetrahedra, and  an edgeedge with one Na(2)O4 tetrahedra. Both Mn(1)-O(1) bond lengths are 2.18 Å. Both Mn(1)-O(2) bond lengths are 2.12 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to four equivalent Na(1) and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), two equivalent Na(3), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing ONa6Mn pentagonal bipyramids.