NaV4Mn3O12 crystallizes in the triclinic P1 space group. Na(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), one O(8), and one O(9) atom to form NaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra, faces with two equivalent V(2)O6 octahedra, faces with two equivalent V(3)O6 octahedra, and faces with two equivalent V(4)O6 octahedra. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(11), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 31-34°. In the second V site, V(2) is bonded to one O(12), one O(2), one O(3), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 31-34°. In the third V site, V(3) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 31-34°. In the fourth V site, V(4) is bonded to one O(1), one O(12), one O(4), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 34°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Mn site, Mn(2) is bonded in a distorted square co-planar geometry to one O(5), one O(6), one O(7), and one O(8) atom. In the third Mn site, Mn(3) is bonded in a distorted square co-planar geometry to one O(10), one O(11), one O(12), and one O(9) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(4), and one Mn(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(3), and one Mn(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(3), and one Mn(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(4), and one Mn(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one V(3), one V(4), and one Mn(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(2), and one Mn(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(2), and one Mn(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one V(3), one V(4), and one Mn(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(4), and one Mn(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(3), and one Mn(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(3), and one Mn(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(4), and one Mn(3) atom.
NaV4Mn3O12 crystallizes in the triclinic P1 space group. Na(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), one O(3), one O(4), one O(5), one O(6), one O(7), one O(8), and one O(9) atom to form NaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra, faces with two equivalent V(2)O6 octahedra, faces with two equivalent V(3)O6 octahedra, and faces with two equivalent V(4)O6 octahedra. The Na(1)-O(1) bond length is 2.68 Å. The Na(1)-O(10) bond length is 2.69 Å. The Na(1)-O(11) bond length is 2.69 Å. The Na(1)-O(12) bond length is 2.68 Å. The Na(1)-O(2) bond length is 2.70 Å. The Na(1)-O(3) bond length is 2.69 Å. The Na(1)-O(4) bond length is 2.68 Å. The Na(1)-O(5) bond length is 2.68 Å. The Na(1)-O(6) bond length is 2.70 Å. The Na(1)-O(7) bond length is 2.70 Å. The Na(1)-O(8) bond length is 2.68 Å. The Na(1)-O(9) bond length is 2.68 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(11), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 31-34°. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(10) bond length is 1.88 Å. The V(1)-O(11) bond length is 1.88 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(6) bond length is 2.02 Å. The V(1)-O(7) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(12), one O(2), one O(3), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 31-34°. The V(2)-O(12) bond length is 2.00 Å. The V(2)-O(2) bond length is 2.02 Å. The V(2)-O(3) bond length is 2.02 Å. The V(2)-O(6) bond length is 1.88 Å. The V(2)-O(7) bond length is 1.88 Å. The V(2)-O(9) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(10), one O(11), one O(2), one O(3), one O(5), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 31-34°. The V(3)-O(10) bond length is 2.02 Å. The V(3)-O(11) bond length is 2.02 Å. The V(3)-O(2) bond length is 1.88 Å. The V(3)-O(3) bond length is 1.88 Å. The V(3)-O(5) bond length is 2.00 Å. The V(3)-O(8) bond length is 2.00 Å. In the fourth V site, V(4) is bonded to one O(1), one O(12), one O(4), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 34°. The V(4)-O(1) bond length is 1.92 Å. The V(4)-O(12) bond length is 1.92 Å. The V(4)-O(4) bond length is 1.92 Å. The V(4)-O(5) bond length is 1.92 Å. The V(4)-O(8) bond length is 1.92 Å. The V(4)-O(9) bond length is 1.92 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted square co-planar geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Mn(1)-O(1) bond length is 2.09 Å. The Mn(1)-O(2) bond length is 2.12 Å. The Mn(1)-O(3) bond length is 2.12 Å. The Mn(1)-O(4) bond length is 2.09 Å. In the second Mn site, Mn(2) is bonded in a distorted square co-planar geometry to one O(5), one O(6), one O(7), and one O(8) atom. The Mn(2)-O(5) bond length is 2.09 Å. The Mn(2)-O(6) bond length is 2.12 Å. The Mn(2)-O(7) bond length is 2.12 Å. The Mn(2)-O(8) bond length is 2.09 Å. In the third Mn site, Mn(3) is bonded in a distorted square co-planar geometry to one O(10), one O(11), one O(12), and one O(9) atom. The Mn(3)-O(10) bond length is 2.12 Å. The Mn(3)-O(11) bond length is 2.12 Å. The Mn(3)-O(12) bond length is 2.09 Å. The Mn(3)-O(9) bond length is 2.09 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(4), and one Mn(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(3), and one Mn(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(3), and one Mn(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(4), and one Mn(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one V(3), one V(4), and one Mn(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(2), and one Mn(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(2), and one Mn(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one V(3), one V(4), and one Mn(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(4), and one Mn(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(3), and one Mn(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(3), and one Mn(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(4), and one Mn(3) atom.