NaV4Mn3O12 crystallizes in the triclinic P-1 space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms 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 two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms 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 are 40°. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms 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 are 40°. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms 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 are 40°. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms 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 40°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Mn site, Mn(2) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(4) atoms. In the third Mn site, Mn(3) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. There are six 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(3), one V(4), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(2), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(4), and one Mn(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(3), and one Mn(3) atom.
NaV4Mn3O12 crystallizes in the triclinic P-1 space group. Na(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms 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. Both Na(1)-O(1) bond lengths are 2.72 Å. Both Na(1)-O(2) bond lengths are 2.71 Å. Both Na(1)-O(3) bond lengths are 2.70 Å. Both Na(1)-O(4) bond lengths are 2.69 Å. Both Na(1)-O(5) bond lengths are 2.68 Å. Both Na(1)-O(6) bond lengths are 2.70 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms 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 are 40°. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(4) bond lengths are 2.00 Å. Both V(1)-O(6) bond lengths are 1.94 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms 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 are 40°. Both V(2)-O(2) bond lengths are 1.97 Å. Both V(2)-O(4) bond lengths are 1.99 Å. Both V(2)-O(5) bond lengths are 1.94 Å. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms 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 are 40°. Both V(3)-O(2) bond lengths are 2.03 Å. Both V(3)-O(3) bond lengths are 1.99 Å. Both V(3)-O(6) bond lengths are 2.04 Å. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms 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 40°. Both V(4)-O(1) bond lengths are 2.03 Å. Both V(4)-O(3) bond lengths are 2.01 Å. Both V(4)-O(5) bond lengths are 2.03 Å. There are three inequivalent Mn sites. In the first Mn site, 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 1.96 Å. Both Mn(1)-O(2) bond lengths are 1.96 Å. In the second Mn site, Mn(2) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(4) atoms. Both Mn(2)-O(3) bond lengths are 1.97 Å. Both Mn(2)-O(4) bond lengths are 1.97 Å. In the third Mn site, Mn(3) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. Both Mn(3)-O(5) bond lengths are 1.98 Å. Both Mn(3)-O(6) bond lengths are 1.97 Å. There are six 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(3), one V(4), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(2), and one Mn(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one V(2), one V(4), and one Mn(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(1), one V(3), and one Mn(3) atom.