NaMn8O16 crystallizes in the monoclinic Pc space group. Na(1) is bonded in a square co-planar geometry to one O(12), one O(14), one O(15), and one O(9) atom. There are eight inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(10), one O(14), one O(4), one O(7), one O(8), and one O(9) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the second Mn site, Mn(2) is bonded to one O(10), one O(13), one O(3), one O(7), one O(8), and one O(9) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the third Mn site, Mn(3) is bonded to one O(11), one O(12), one O(15), one O(5), one O(6), and one O(8) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the fourth Mn site, Mn(4) is bonded to one O(11), one O(12), one O(16), one O(5), one O(6), and one O(7) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(11), one O(15), one O(16), one O(3), and one O(4) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the sixth Mn site, Mn(6) is bonded to one O(12), one O(15), one O(16), one O(2), one O(3), and one O(4) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the seventh Mn site, Mn(7) is bonded to one O(1), one O(10), one O(13), one O(14), one O(2), and one O(5) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the eighth Mn site, Mn(8) is bonded to one O(1), one O(13), one O(14), one O(2), one O(6), and one O(9) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(5), one Mn(7), and one Mn(8) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(6), one Mn(7), and one Mn(8) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(5), and one Mn(6) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(4), and one Mn(7) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mn(3), one Mn(4), and one Mn(8) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Mn(1), one Mn(2), and one Mn(8) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(7) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Mn(3), one Mn(4), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing ONaMn3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(7), and one Mn(8) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Mn(1), one Mn(7), and one Mn(8) atom. In the fifteenth O site, O(15) is bonded to one Na(1), one Mn(3), one Mn(5), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing ONaMn3 tetrahedra. In the sixteenth O site, O(16) is bonded in a distorted trigonal non-coplanar geometry to one Mn(4), one Mn(5), and one Mn(6) atom.
NaMn8O16 crystallizes in the monoclinic Pc space group. Na(1) is bonded in a square co-planar geometry to one O(12), one O(14), one O(15), and one O(9) atom. The Na(1)-O(12) bond length is 2.46 Å. The Na(1)-O(14) bond length is 2.46 Å. The Na(1)-O(15) bond length is 2.47 Å. The Na(1)-O(9) bond length is 2.47 Å. There are eight inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(10), one O(14), one O(4), one O(7), one O(8), and one O(9) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Mn(1)-O(10) bond length is 1.91 Å. The Mn(1)-O(14) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.88 Å. The Mn(1)-O(7) bond length is 1.88 Å. The Mn(1)-O(8) bond length is 1.89 Å. The Mn(1)-O(9) bond length is 1.93 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(13), one O(3), one O(7), one O(8), and one O(9) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(2)-O(10) bond length is 1.91 Å. The Mn(2)-O(13) bond length is 1.92 Å. The Mn(2)-O(3) bond length is 1.89 Å. The Mn(2)-O(7) bond length is 1.89 Å. The Mn(2)-O(8) bond length is 1.89 Å. The Mn(2)-O(9) bond length is 1.93 Å. In the third Mn site, Mn(3) is bonded to one O(11), one O(12), one O(15), one O(5), one O(6), and one O(8) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(3)-O(11) bond length is 1.91 Å. The Mn(3)-O(12) bond length is 1.93 Å. The Mn(3)-O(15) bond length is 1.94 Å. The Mn(3)-O(5) bond length is 1.88 Å. The Mn(3)-O(6) bond length is 1.89 Å. The Mn(3)-O(8) bond length is 1.89 Å. In the fourth Mn site, Mn(4) is bonded to one O(11), one O(12), one O(16), one O(5), one O(6), and one O(7) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Mn(4)-O(11) bond length is 1.91 Å. The Mn(4)-O(12) bond length is 1.93 Å. The Mn(4)-O(16) bond length is 1.92 Å. The Mn(4)-O(5) bond length is 1.88 Å. The Mn(4)-O(6) bond length is 1.89 Å. The Mn(4)-O(7) bond length is 1.89 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(11), one O(15), one O(16), one O(3), and one O(4) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Mn(5)-O(1) bond length is 1.89 Å. The Mn(5)-O(11) bond length is 1.92 Å. The Mn(5)-O(15) bond length is 1.93 Å. The Mn(5)-O(16) bond length is 1.91 Å. The Mn(5)-O(3) bond length is 1.88 Å. The Mn(5)-O(4) bond length is 1.89 Å. In the sixth Mn site, Mn(6) is bonded to one O(12), one O(15), one O(16), one O(2), one O(3), and one O(4) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(6)-O(12) bond length is 1.94 Å. The Mn(6)-O(15) bond length is 1.93 Å. The Mn(6)-O(16) bond length is 1.91 Å. The Mn(6)-O(2) bond length is 1.88 Å. The Mn(6)-O(3) bond length is 1.88 Å. The Mn(6)-O(4) bond length is 1.89 Å. In the seventh Mn site, Mn(7) is bonded to one O(1), one O(10), one O(13), one O(14), one O(2), and one O(5) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(7)-O(1) bond length is 1.88 Å. The Mn(7)-O(10) bond length is 1.92 Å. The Mn(7)-O(13) bond length is 1.91 Å. The Mn(7)-O(14) bond length is 1.93 Å. The Mn(7)-O(2) bond length is 1.89 Å. The Mn(7)-O(5) bond length is 1.89 Å. In the eighth Mn site, Mn(8) is bonded to one O(1), one O(13), one O(14), one O(2), one O(6), and one O(9) atom to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Mn(8)-O(1) bond length is 1.88 Å. The Mn(8)-O(13) bond length is 1.91 Å. The Mn(8)-O(14) bond length is 1.93 Å. The Mn(8)-O(2) bond length is 1.89 Å. The Mn(8)-O(6) bond length is 1.88 Å. The Mn(8)-O(9) bond length is 1.94 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(5), one Mn(7), and one Mn(8) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(6), one Mn(7), and one Mn(8) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(5), and one Mn(6) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(1), one Mn(5), and one Mn(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(4), and one Mn(7) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mn(3), one Mn(4), and one Mn(8) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Mn(1), one Mn(2), and one Mn(8) atom. In the tenth O site, O(10) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one Mn(7) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Mn(3), one Mn(4), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing ONaMn3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(7), and one Mn(8) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Mn(1), one Mn(7), and one Mn(8) atom. In the fifteenth O site, O(15) is bonded to one Na(1), one Mn(3), one Mn(5), and one Mn(6) atom to form a mixture of distorted corner and edge-sharing ONaMn3 tetrahedra. In the sixteenth O site, O(16) is bonded in a distorted trigonal non-coplanar geometry to one Mn(4), one Mn(5), and one Mn(6) atom.