Mg1VO2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted edge-sharing MgO5 trigonal bipyramids. In the second Mg site, Mg(2) is bonded in a rectangular see-saw-like geometry to one O(3), one O(4), and two equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(2), and two equivalent V(1) atoms to form distorted OMgV3 tetrahedra that share corners with four equivalent O(2)Mg2V3 square pyramids, corners with two equivalent O(1)MgV3 tetrahedra, corners with four equivalent O(3)Mg3V2 trigonal bipyramids, and  an edgeedge with one O(3)Mg3V2 trigonal bipyramid. In the second O site, O(2) is bonded to two equivalent Mg(2), one V(1), and two equivalent V(2) atoms to form OMg2V3 square pyramids that share corners with four equivalent O(1)MgV3 tetrahedra, edges with two equivalent O(2)Mg2V3 square pyramids, and edges with two equivalent O(3)Mg3V2 trigonal bipyramids. In the third O site, O(3) is bonded to one Mg(2), two equivalent Mg(1), and two equivalent V(1) atoms to form distorted OMg3V2 trigonal bipyramids that share corners with four equivalent O(1)MgV3 tetrahedra, edges with two equivalent O(2)Mg2V3 square pyramids,  an edgeedge with one O(1)MgV3 tetrahedra, and edges with two equivalent O(3)Mg3V2 trigonal bipyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Mg(2), two equivalent Mg(1), and two equivalent V(2) atoms.
Mg1VO2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted edge-sharing MgO5 trigonal bipyramids. The Mg(1)-O(1) bond length is 1.98 Å. Both Mg(1)-O(3) bond lengths are 2.09 Å. Both Mg(1)-O(4) bond lengths are 2.17 Å. In the second Mg site, Mg(2) is bonded in a rectangular see-saw-like geometry to one O(3), one O(4), and two equivalent O(2) atoms. The Mg(2)-O(3) bond length is 1.99 Å. The Mg(2)-O(4) bond length is 1.97 Å. Both Mg(2)-O(2) bond lengths are 2.08 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. The V(1)-O(2) bond length is 2.15 Å. Both V(1)-O(1) bond lengths are 2.06 Å. Both V(1)-O(3) bond lengths are 2.18 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. The V(2)-O(1) bond length is 2.02 Å. Both V(2)-O(2) bond lengths are 2.11 Å. Both V(2)-O(4) bond lengths are 2.15 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(2), and two equivalent V(1) atoms to form distorted OMgV3 tetrahedra that share corners with four equivalent O(2)Mg2V3 square pyramids, corners with two equivalent O(1)MgV3 tetrahedra, corners with four equivalent O(3)Mg3V2 trigonal bipyramids, and  an edgeedge with one O(3)Mg3V2 trigonal bipyramid. In the second O site, O(2) is bonded to two equivalent Mg(2), one V(1), and two equivalent V(2) atoms to form OMg2V3 square pyramids that share corners with four equivalent O(1)MgV3 tetrahedra, edges with two equivalent O(2)Mg2V3 square pyramids, and edges with two equivalent O(3)Mg3V2 trigonal bipyramids. In the third O site, O(3) is bonded to one Mg(2), two equivalent Mg(1), and two equivalent V(1) atoms to form distorted OMg3V2 trigonal bipyramids that share corners with four equivalent O(1)MgV3 tetrahedra, edges with two equivalent O(2)Mg2V3 square pyramids,  an edgeedge with one O(1)MgV3 tetrahedra, and edges with two equivalent O(3)Mg3V2 trigonal bipyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Mg(2), two equivalent Mg(1), and two equivalent V(2) atoms.