Na5MnO4 crystallizes in the orthorhombic Pmn2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted NaO4 tetrahedra that share corners with four equivalent Mn(1)O4 trigonal pyramids. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), and two equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. Mn(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted MnO4 trigonal pyramids that share corners with four equivalent Na(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 8-coordinate geometry to one Na(1), two equivalent Na(2), four equivalent Na(3), and one Mn(1) atom. In the second O site, O(2) is bonded to one 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 ONa5Mn pentagonal pyramids. The corner-sharing octahedral tilt angles range from 67-68°. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(3), and one Mn(1) atom to form a mixture of corner and edge-sharing ONa5Mn octahedra. The corner-sharing octahedral tilt angles range from 45-49°.
Na5MnO4 crystallizes in the orthorhombic Pmn2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted NaO4 tetrahedra that share corners with four equivalent Mn(1)O4 trigonal pyramids. The Na(1)-O(1) bond length is 2.44 Å. The Na(1)-O(2) bond length is 2.38 Å. Both Na(1)-O(3) bond lengths are 2.30 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Na(2)-O(1) bond length is 2.35 Å. The Na(2)-O(2) bond length is 2.43 Å. There is one shorter (2.24 Å) and one longer (2.26 Å) Na(2)-O(3) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. The Na(3)-O(2) bond length is 2.38 Å. There is one shorter (2.58 Å) and one longer (2.68 Å) Na(3)-O(1) bond length. There is one shorter (2.28 Å) and one longer (2.29 Å) Na(3)-O(3) bond length. Mn(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted MnO4 trigonal pyramids that share corners with four equivalent Na(1)O4 tetrahedra. The Mn(1)-O(1) bond length is 1.89 Å. The Mn(1)-O(2) bond length is 1.85 Å. Both Mn(1)-O(3) bond lengths are 1.88 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 8-coordinate geometry to one Na(1), two equivalent Na(2), four equivalent Na(3), and one Mn(1) atom. In the second O site, O(2) is bonded to one 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 ONa5Mn pentagonal pyramids. The corner-sharing octahedral tilt angles range from 67-68°. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(3), and one Mn(1) atom to form a mixture of corner and edge-sharing ONa5Mn octahedra. The corner-sharing octahedral tilt angles range from 45-49°.