MgV5O12 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(4), and one O(7) atom to form distorted MgO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(5)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-60°. There are five 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 two equivalent Mg(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-58°. 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 5-coordinate geometry to one O(1), 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 V(5)O6 octahedra, corners with four equivalent V(1)O6 octahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-61°. In the fifth V site, V(5) 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 distorted VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent Mg(1)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-61°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(2), one V(3), and one V(5) atom to form distorted edge-sharing OMgV3 trigonal pyramids. 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 distorted trigonal planar geometry to one Mg(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded to one Mg(1), one V(2), one V(3), and one V(5) atom to form distorted edge-sharing OMgV3 trigonal pyramids. 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 4-coordinate geometry to one Mg(1), one V(2), one V(4), and one V(5) 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 V(5) 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 V(5) atom. In the tenth O site, O(10) is bonded in a 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 trigonal planar geometry to one Mg(1), one V(1), and one V(5) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one V(3) atom.
MgV5O12 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(4), and one O(7) atom to form distorted MgO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(5)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-60°. The Mg(1)-O(1) bond length is 2.03 Å. The Mg(1)-O(11) bond length is 2.05 Å. The Mg(1)-O(12) bond length is 2.19 Å. The Mg(1)-O(3) bond length is 2.04 Å. The Mg(1)-O(4) bond length is 2.16 Å. The Mg(1)-O(7) bond length is 2.14 Å. There are five 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 two equivalent Mg(1)O6 octahedra, corners with four equivalent V(4)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-58°. The V(1)-O(10) bond length is 2.07 Å. The V(1)-O(11) bond length is 1.89 Å. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(3) bond length is 1.77 Å. The V(1)-O(5) bond length is 1.68 Å. The V(1)-O(8) bond length is 2.15 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 1.99 Å. The V(2)-O(12) bond length is 2.04 Å. The V(2)-O(4) bond length is 2.03 Å. The V(2)-O(6) bond length is 1.68 Å. The V(2)-O(7) bond length is 2.49 Å. The V(2)-O(9) bond length is 1.97 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(2), one O(4), and one O(9) atom. The V(3)-O(1) bond length is 2.10 Å. The V(3)-O(12) bond length is 1.75 Å. The V(3)-O(2) bond length is 1.69 Å. The V(3)-O(4) bond length is 2.00 Å. The V(3)-O(9) bond length is 1.87 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 V(5)O6 octahedra, corners with four equivalent V(1)O6 octahedra, and  an edgeedge with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-61°. The V(4)-O(10) bond length is 1.69 Å. The V(4)-O(3) bond length is 2.10 Å. The V(4)-O(5) bond length is 2.02 Å. The V(4)-O(6) bond length is 1.98 Å. The V(4)-O(7) bond length is 2.09 Å. The V(4)-O(8) bond length is 1.96 Å. In the fifth V site, V(5) 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 distorted VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent Mg(1)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-61°. The V(5)-O(1) bond length is 2.06 Å. The V(5)-O(11) bond length is 1.95 Å. The V(5)-O(4) bond length is 2.11 Å. The V(5)-O(7) bond length is 1.82 Å. The V(5)-O(8) bond length is 1.88 Å. The V(5)-O(9) bond length is 2.07 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(2), one V(3), and one V(5) atom to form distorted edge-sharing OMgV3 trigonal pyramids. 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 distorted trigonal planar geometry to one Mg(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded to one Mg(1), one V(2), one V(3), and one V(5) atom to form distorted edge-sharing OMgV3 trigonal pyramids. 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 4-coordinate geometry to one Mg(1), one V(2), one V(4), and one V(5) 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 V(5) 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 V(5) atom. In the tenth O site, O(10) is bonded in a 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 trigonal planar geometry to one Mg(1), one V(1), and one V(5) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Mg(1), one V(2), and one V(3) atom.