V4MnO12 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) 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 distorted VO6 octahedra that share corners with four equivalent V(4)O6 octahedra and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-51°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom. In the fourth V site, V(4) is bonded to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-56°. Mn(1) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent V(4)O6 octahedra and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2), one V(3), 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(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Mn(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one Mn(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Mn(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Mn(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one Mn(1) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom.
V4MnO12 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) 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 distorted VO6 octahedra that share corners with four equivalent V(4)O6 octahedra and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-51°. The V(1)-O(10) bond length is 2.25 Å. The V(1)-O(11) bond length is 1.90 Å. The V(1)-O(2) bond length is 2.02 Å. The V(1)-O(3) bond length is 1.67 Å. The V(1)-O(5) bond length is 1.71 Å. The V(1)-O(8) bond length is 2.16 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(4), one O(6), one O(7), and one O(9) atom. The V(2)-O(1) bond length is 1.88 Å. The V(2)-O(12) bond length is 1.93 Å. The V(2)-O(4) bond length is 2.04 Å. The V(2)-O(6) bond length is 1.65 Å. The V(2)-O(7) bond length is 2.32 Å. The V(2)-O(9) bond length is 1.85 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom. The V(3)-O(1) bond length is 2.12 Å. The V(3)-O(11) bond length is 2.26 Å. The V(3)-O(12) bond length is 1.72 Å. The V(3)-O(2) bond length is 1.70 Å. The V(3)-O(4) bond length is 1.87 Å. The V(3)-O(9) bond length is 2.09 Å. In the fourth V site, V(4) is bonded to one O(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-56°. The V(4)-O(10) bond length is 1.66 Å. The V(4)-O(3) bond length is 2.13 Å. The V(4)-O(5) bond length is 1.96 Å. The V(4)-O(6) bond length is 2.18 Å. The V(4)-O(7) bond length is 1.79 Å. The V(4)-O(8) bond length is 1.89 Å. Mn(1) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent V(4)O6 octahedra and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. The Mn(1)-O(1) bond length is 1.90 Å. The Mn(1)-O(11) bond length is 1.86 Å. The Mn(1)-O(4) bond length is 2.00 Å. The Mn(1)-O(7) bond length is 1.93 Å. The Mn(1)-O(8) bond length is 1.91 Å. The Mn(1)-O(9) bond length is 1.94 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2), one V(3), 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(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Mn(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one Mn(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Mn(1) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one Mn(1) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one Mn(1) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom.