MgV2O5 crystallizes in the orthorhombic Cmcm space group. Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. V(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), and three equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1) and two equivalent V(1) atoms to form OMg2V2 tetrahedra that share corners with two equivalent O(1)Mg2V2 tetrahedra, corners with two equivalent O(2)MgV3 trigonal pyramids, and edges with four equivalent O(2)MgV3 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1) and three equivalent V(1) atoms to form distorted OMgV3 trigonal pyramids that share  a cornercorner with one O(1)Mg2V2 tetrahedra, corners with three equivalent O(2)MgV3 trigonal pyramids, edges with two equivalent O(1)Mg2V2 tetrahedra, and edges with two equivalent O(2)MgV3 trigonal pyramids. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(1) atom.
MgV2O5 crystallizes in the orthorhombic Cmcm space group. Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Mg(1)-O(1) bond lengths are 2.06 Å. Both Mg(1)-O(2) bond lengths are 2.33 Å. Both Mg(1)-O(3) bond lengths are 2.05 Å. V(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), and three equivalent O(2) atoms. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.66 Å. There are two shorter (1.98 Å) and one longer (2.00 Å) V(1)-O(2) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1) and two equivalent V(1) atoms to form OMg2V2 tetrahedra that share corners with two equivalent O(1)Mg2V2 tetrahedra, corners with two equivalent O(2)MgV3 trigonal pyramids, and edges with four equivalent O(2)MgV3 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1) and three equivalent V(1) atoms to form distorted OMgV3 trigonal pyramids that share  a cornercorner with one O(1)Mg2V2 tetrahedra, corners with three equivalent O(2)MgV3 trigonal pyramids, edges with two equivalent O(1)Mg2V2 tetrahedra, and edges with two equivalent O(2)MgV3 trigonal pyramids. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mg(1) and one V(1) atom.