NaV4Mn3O12 crystallizes in the trigonal R-3 space group. Na(1) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form NaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra and faces with six equivalent V(2)O6 octahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(2)O6 octahedra and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 37°. In the second V site, V(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-38°. Mn(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. There are two 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(2), and one Mn(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), two equivalent V(2), and one Mn(1) atom.
NaV4Mn3O12 crystallizes in the trigonal R-3 space group. Na(1) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form NaO12 cuboctahedra that share faces with two equivalent V(1)O6 octahedra and faces with six equivalent V(2)O6 octahedra. All Na(1)-O(1) bond lengths are 2.68 Å. All Na(1)-O(2) bond lengths are 2.70 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent V(2)O6 octahedra and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 37°. All V(1)-O(1) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, and faces with two equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 37-38°. Both V(2)-O(1) bond lengths are 1.93 Å. There are two shorter (1.98 Å) and two longer (1.99 Å) V(2)-O(2) bond lengths. 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 2.03 Å. Both Mn(1)-O(2) bond lengths are 1.99 Å. There are two 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(2), and one Mn(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), two equivalent V(2), and one Mn(1) atom.