MgV3O6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form MgO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-75°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 7-22°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent Mg(1)O5 trigonal bipyramids, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 7-22°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 20-21°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(3) 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(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a trigonal pyramidal geometry to one Mg(1), one V(1), one V(2), and one V(3) atom.
MgV3O6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form MgO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-75°. The Mg(1)-O(1) bond length is 1.98 Å. The Mg(1)-O(2) bond length is 2.14 Å. The Mg(1)-O(4) bond length is 2.16 Å. The Mg(1)-O(5) bond length is 2.04 Å. The Mg(1)-O(6) bond length is 1.99 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 7-22°. The V(1)-O(1) bond length is 2.05 Å. The V(1)-O(2) bond length is 2.16 Å. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(4) bond length is 2.00 Å. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent Mg(1)O5 trigonal bipyramids, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 7-22°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(2) bond length is 2.10 Å. The V(2)-O(3) bond length is 2.00 Å. The V(2)-O(4) bond length is 1.99 Å. The V(2)-O(5) bond length is 2.06 Å. The V(2)-O(6) bond length is 2.09 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 20-21°. The V(3)-O(1) bond length is 2.01 Å. The V(3)-O(2) bond length is 1.86 Å. The V(3)-O(3) bond length is 1.93 Å. The V(3)-O(4) bond length is 2.28 Å. The V(3)-O(5) bond length is 1.98 Å. The V(3)-O(6) bond length is 1.98 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Mg(1), one V(1), one V(2), and one V(3) 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(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a trigonal pyramidal geometry to one Mg(1), one V(1), one V(2), and one V(3) atom.