MgV5O10 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one O(5), one O(6), one O(7), and one O(9) atom to form MgO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-65°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-28°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 13-28°. In the third V site, V(3) is bonded to one O(10), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(5)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-28°. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 14-21°. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-28°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one V(2), one V(4), and one V(5) atom. In the second O site, O(2) is bonded in a see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(5) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(5) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Mg(1), one V(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 V(2), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(3), and one V(5) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom.
MgV5O10 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one O(5), one O(6), one O(7), and one O(9) atom to form MgO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-65°. The Mg(1)-O(2) bond length is 2.00 Å. The Mg(1)-O(5) bond length is 2.01 Å. The Mg(1)-O(6) bond length is 2.03 Å. The Mg(1)-O(7) bond length is 1.98 Å. The Mg(1)-O(9) bond length is 2.04 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-28°. The V(1)-O(2) bond length is 2.13 Å. The V(1)-O(3) bond length is 2.12 Å. The V(1)-O(5) bond length is 2.00 Å. The V(1)-O(6) bond length is 2.06 Å. The V(1)-O(7) bond length is 2.10 Å. The V(1)-O(9) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(2), one O(4), one O(6), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 13-28°. The V(2)-O(1) bond length is 1.87 Å. The V(2)-O(10) bond length is 1.95 Å. The V(2)-O(2) bond length is 2.09 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(6) bond length is 1.92 Å. The V(2)-O(8) bond length is 2.25 Å. In the third V site, V(3) is bonded to one O(10), one O(3), one O(4), one O(5), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(5)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-28°. The V(3)-O(10) bond length is 1.96 Å. The V(3)-O(3) bond length is 1.83 Å. The V(3)-O(4) bond length is 2.01 Å. The V(3)-O(5) bond length is 2.16 Å. The V(3)-O(7) bond length is 1.91 Å. The V(3)-O(9) bond length is 2.08 Å. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 14-21°. The V(4)-O(1) bond length is 1.98 Å. The V(4)-O(10) bond length is 2.01 Å. The V(4)-O(4) bond length is 2.02 Å. The V(4)-O(5) bond length is 1.99 Å. The V(4)-O(7) bond length is 2.17 Å. The V(4)-O(8) bond length is 1.80 Å. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-28°. The V(5)-O(1) bond length is 2.04 Å. The V(5)-O(2) bond length is 1.94 Å. The V(5)-O(3) bond length is 2.01 Å. The V(5)-O(6) bond length is 2.08 Å. The V(5)-O(8) bond length is 1.97 Å. The V(5)-O(9) bond length is 2.24 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one V(2), one V(4), and one V(5) atom. In the second O site, O(2) is bonded in a see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(5) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(5) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Mg(1), one V(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 V(2), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(3), and one V(5) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one V(2), one V(3), and one V(4) atom.