V5MnO12 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent V(3)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-59°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-59°. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Mn(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one Mn(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one Mn(1) atom.
V5MnO12 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent V(3)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.14 Å. Both V(1)-O(2) bond lengths are 2.07 Å. Both V(1)-O(3) bond lengths are 2.13 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-59°. The V(2)-O(1) bond length is 1.74 Å. The V(2)-O(2) bond length is 1.69 Å. The V(2)-O(4) bond length is 1.80 Å. The V(2)-O(5) bond length is 1.80 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-59°. The V(3)-O(3) bond length is 1.74 Å. The V(3)-O(4) bond length is 1.79 Å. The V(3)-O(5) bond length is 1.80 Å. The V(3)-O(6) bond length is 1.68 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both Mn(1)-O(1) bond lengths are 2.26 Å. Both Mn(1)-O(3) bond lengths are 2.20 Å. Both Mn(1)-O(6) bond lengths are 2.12 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Mn(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one Mn(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one Mn(1) atom.