MgV5O12 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), and one O(8) atom. 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 a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 25-50°. 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 corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 25-59°. 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 a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. 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 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 trigonal planar geometry to one Mg(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(5) 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 distorted rectangular see-saw-like 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 to one Mg(1), one V(1), one V(4), and one V(5) atom to form edge-sharing OMgV3 trigonal pyramids. 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 distorted T-shaped geometry to one Mg(1), one V(1), and one V(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Mg(1), one V(1), one V(3), and one V(5) 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.
MgV5O12 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), and one O(8) atom. The Mg(1)-O(1) bond length is 1.98 Å. The Mg(1)-O(10) bond length is 2.36 Å. The Mg(1)-O(11) bond length is 1.99 Å. The Mg(1)-O(3) bond length is 1.99 Å. The Mg(1)-O(7) bond length is 2.43 Å. The Mg(1)-O(8) bond length is 2.21 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 a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 25-50°. The V(1)-O(10) bond length is 2.06 Å. The V(1)-O(11) bond length is 1.94 Å. The V(1)-O(2) bond length is 1.89 Å. The V(1)-O(3) bond length is 1.79 Å. The V(1)-O(5) bond length is 1.68 Å. The V(1)-O(8) bond length is 2.24 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 2.02 Å. The V(2)-O(4) bond length is 2.00 Å. The V(2)-O(6) bond length is 1.70 Å. The V(2)-O(7) bond length is 2.27 Å. The V(2)-O(9) bond length is 2.02 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 2.20 Å. The V(3)-O(11) bond length is 2.39 Å. The V(3)-O(12) bond length is 1.70 Å. The V(3)-O(2) bond length is 1.74 Å. The V(3)-O(4) 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(10), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 25-59°. The V(4)-O(10) bond length is 1.73 Å. The V(4)-O(3) bond length is 2.02 Å. The V(4)-O(5) bond length is 2.02 Å. The V(4)-O(6) bond length is 1.94 Å. The V(4)-O(7) bond length is 2.11 Å. The V(4)-O(8) bond length is 1.98 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 a mixture of distorted edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 47-59°. The V(5)-O(1) bond length is 2.02 Å. The V(5)-O(11) bond length is 2.01 Å. The V(5)-O(4) bond length is 2.04 Å. The V(5)-O(7) bond length is 1.83 Å. The V(5)-O(8) bond length is 1.94 Å. The V(5)-O(9) bond length is 2.02 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 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 trigonal planar geometry to one Mg(1), one V(1), and one V(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(5) 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 distorted rectangular see-saw-like 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 to one Mg(1), one V(1), one V(4), and one V(5) atom to form edge-sharing OMgV3 trigonal pyramids. 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 distorted T-shaped geometry to one Mg(1), one V(1), and one V(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Mg(1), one V(1), one V(3), and one V(5) 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.