Mg2VWO6 crystallizes in the monoclinic P2_1/c space group. Mg(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. W(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form WO6 octahedra that share corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one W(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one W(1) atom. In the third O site, O(3) is bonded to two equivalent Mg(1), one V(1), and one W(1) atom to form distorted corner-sharing OMg2VW trigonal pyramids.
Mg2VWO6 crystallizes in the monoclinic P2_1/c space group. Mg(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Mg(1)-O(1) bond length is 2.06 Å. The Mg(1)-O(2) bond length is 2.07 Å. There is one shorter (2.06 Å) and one longer (2.13 Å) Mg(1)-O(3) bond length. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. Both V(1)-O(1) bond lengths are 2.01 Å. Both V(1)-O(2) bond lengths are 2.03 Å. Both V(1)-O(3) bond lengths are 2.10 Å. W(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form WO6 octahedra that share corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. Both W(1)-O(1) bond lengths are 2.02 Å. Both W(1)-O(2) bond lengths are 1.99 Å. Both W(1)-O(3) bond lengths are 2.04 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one W(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mg(1), one V(1), and one W(1) atom. In the third O site, O(3) is bonded to two equivalent Mg(1), one V(1), and one W(1) atom to form distorted corner-sharing OMg2VW trigonal pyramids.