MgV2O6 crystallizes in the orthorhombic Pbcn space group. Mg(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted edge-sharing MgO6 octahedra. V(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(1), and three equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mg(1) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Mg(1) and one V(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms.
MgV2O6 crystallizes in the orthorhombic Pbcn space group. Mg(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted edge-sharing MgO6 octahedra. Both Mg(1)-O(1) bond lengths are 2.05 Å. There are two shorter (2.06 Å) and two longer (2.16 Å) Mg(1)-O(2) bond lengths. V(1) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(1), and three equivalent O(3) atoms. The V(1)-O(2) bond length is 1.68 Å. There is one shorter (1.77 Å) and one longer (2.02 Å) V(1)-O(1) bond length. There are a spread of V(1)-O(3) bond distances ranging from 1.77-2.25 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mg(1) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Mg(1) and one V(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to three equivalent V(1) atoms.