MgV4Mn2O12 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(10), one O(11), one O(4), one O(7), and one O(8) atom to form distorted MgO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra,  an edgeedge with one V(2)O4 tetrahedra, and  an edgeedge with one V(4)O4 tetrahedra. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mg(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 23-62°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-57°. In the third V site, V(3) is bonded to one O(10), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-62°. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-57°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(5) atom to form MnO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(3), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing OMgMn2V tetrahedra. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Mn(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one Mn(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one Mn(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one Mn(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the tenth O site, O(10) is bonded to one Mg(1), one V(3), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing OMgMn2V tetrahedra. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Mg(1), one V(4), and one Mn(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(4), one Mn(1), and one Mn(2) atom.
MgV4Mn2O12 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(10), one O(11), one O(4), one O(7), and one O(8) atom to form distorted MgO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra,  an edgeedge with one V(2)O4 tetrahedra, and  an edgeedge with one V(4)O4 tetrahedra. The Mg(1)-O(1) bond length is 2.09 Å. The Mg(1)-O(10) bond length is 2.09 Å. The Mg(1)-O(11) bond length is 2.20 Å. The Mg(1)-O(4) bond length is 2.27 Å. The Mg(1)-O(7) bond length is 2.26 Å. The Mg(1)-O(8) bond length is 2.19 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mg(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 23-62°. The V(1)-O(1) bond length is 1.84 Å. The V(1)-O(2) bond length is 1.69 Å. The V(1)-O(4) bond length is 1.93 Å. The V(1)-O(6) bond length is 1.88 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent V(1)O4 tetrahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-57°. The V(2)-O(3) bond length is 1.73 Å. The V(2)-O(4) bond length is 1.80 Å. The V(2)-O(6) bond length is 1.75 Å. The V(2)-O(8) bond length is 1.73 Å. In the third V site, V(3) is bonded to one O(10), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-62°. The V(3)-O(10) bond length is 1.84 Å. The V(3)-O(5) bond length is 1.69 Å. The V(3)-O(7) bond length is 1.93 Å. The V(3)-O(9) bond length is 1.88 Å. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-57°. The V(4)-O(11) bond length is 1.73 Å. The V(4)-O(12) bond length is 1.73 Å. The V(4)-O(7) bond length is 1.80 Å. The V(4)-O(9) bond length is 1.75 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(5) atom to form MnO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The Mn(1)-O(1) bond length is 2.27 Å. The Mn(1)-O(10) bond length is 2.28 Å. The Mn(1)-O(12) bond length is 2.24 Å. The Mn(1)-O(2) bond length is 2.07 Å. The Mn(1)-O(3) bond length is 2.24 Å. The Mn(1)-O(5) bond length is 2.07 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(11), one O(12), one O(3), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The Mn(2)-O(1) bond length is 2.19 Å. The Mn(2)-O(10) bond length is 2.19 Å. The Mn(2)-O(11) bond length is 2.20 Å. The Mn(2)-O(12) bond length is 2.21 Å. The Mn(2)-O(3) bond length is 2.22 Å. The Mn(2)-O(8) bond length is 2.20 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(1), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing OMgMn2V tetrahedra. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Mn(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one Mn(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one Mn(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mg(1), one V(3), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one Mn(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the tenth O site, O(10) is bonded to one Mg(1), one V(3), one Mn(1), and one Mn(2) atom to form a mixture of distorted corner and edge-sharing OMgMn2V tetrahedra. In the eleventh O site, O(11) is bonded in a distorted T-shaped geometry to one Mg(1), one V(4), and one Mn(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(4), one Mn(1), and one Mn(2) atom.