MgV2Zn4O8 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MgO6 octahedra that share corners with six equivalent Zn(2)O6 octahedra, edges with two equivalent Zn(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. 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 edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Zn(2)O6 octahedra, and edges with two equivalent Zn(3)O6 octahedra. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. In the second Zn site, Zn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZnO6 octahedra that share corners with six equivalent Mg(1)O6 octahedra, edges with two equivalent Zn(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. In the third Zn site, Zn(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form ZnO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent Zn(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(1), one Zn(1), one Zn(2), and one Zn(3) atom to form OMgVZn3 square pyramids that share  a cornercorner with one O(2)MgV2Zn2 square pyramid, corners with five equivalent O(1)MgVZn3 square pyramids, corners with three equivalent O(3)V2Zn2 tetrahedra, edges with three equivalent O(2)MgV2Zn2 square pyramids, edges with three equivalent O(1)MgVZn3 square pyramids, and  an edgeedge with one O(3)V2Zn2 tetrahedra. In the second O site, O(2) is bonded to one Mg(1), two equivalent V(1), one Zn(1), and one Zn(2) atom to form OMgV2Zn2 square pyramids that share corners with two equivalent O(1)MgVZn3 square pyramids, corners with four equivalent O(2)MgV2Zn2 square pyramids, corners with three equivalent O(3)V2Zn2 tetrahedra, edges with six equivalent O(1)MgVZn3 square pyramids, and  an edgeedge with one O(3)V2Zn2 tetrahedra. In the third O site, O(3) is bonded to two equivalent V(1), one Zn(1), and one Zn(3) atom to form distorted OV2Zn2 tetrahedra that share corners with three equivalent O(2)MgV2Zn2 square pyramids, corners with six equivalent O(1)MgVZn3 square pyramids, corners with three equivalent O(3)V2Zn2 tetrahedra,  an edgeedge with one O(2)MgV2Zn2 square pyramid, and edges with two equivalent O(1)MgVZn3 square pyramids.
MgV2Zn4O8 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MgO6 octahedra that share corners with six equivalent Zn(2)O6 octahedra, edges with two equivalent Zn(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Mg(1)-O(2) bond lengths are 2.09 Å. All Mg(1)-O(1) bond lengths are 2.15 Å. 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 edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Zn(2)O6 octahedra, and edges with two equivalent Zn(3)O6 octahedra. Both V(1)-O(1) bond lengths are 2.09 Å. Both V(1)-O(2) bond lengths are 2.12 Å. Both V(1)-O(3) bond lengths are 1.99 Å. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Zn(1)-O(2) bond length is 2.16 Å. The Zn(1)-O(3) bond length is 1.87 Å. Both Zn(1)-O(1) bond lengths are 2.07 Å. In the second Zn site, Zn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZnO6 octahedra that share corners with six equivalent Mg(1)O6 octahedra, edges with two equivalent Zn(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. Both Zn(2)-O(2) bond lengths are 2.29 Å. All Zn(2)-O(1) bond lengths are 2.21 Å. In the third Zn site, Zn(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form ZnO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent Zn(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Both Zn(3)-O(3) bond lengths are 2.04 Å. All Zn(3)-O(1) bond lengths are 2.18 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one V(1), one Zn(1), one Zn(2), and one Zn(3) atom to form OMgVZn3 square pyramids that share  a cornercorner with one O(2)MgV2Zn2 square pyramid, corners with five equivalent O(1)MgVZn3 square pyramids, corners with three equivalent O(3)V2Zn2 tetrahedra, edges with three equivalent O(2)MgV2Zn2 square pyramids, edges with three equivalent O(1)MgVZn3 square pyramids, and  an edgeedge with one O(3)V2Zn2 tetrahedra. In the second O site, O(2) is bonded to one Mg(1), two equivalent V(1), one Zn(1), and one Zn(2) atom to form OMgV2Zn2 square pyramids that share corners with two equivalent O(1)MgVZn3 square pyramids, corners with four equivalent O(2)MgV2Zn2 square pyramids, corners with three equivalent O(3)V2Zn2 tetrahedra, edges with six equivalent O(1)MgVZn3 square pyramids, and  an edgeedge with one O(3)V2Zn2 tetrahedra. In the third O site, O(3) is bonded to two equivalent V(1), one Zn(1), and one Zn(3) atom to form distorted OV2Zn2 tetrahedra that share corners with three equivalent O(2)MgV2Zn2 square pyramids, corners with six equivalent O(1)MgVZn3 square pyramids, corners with three equivalent O(3)V2Zn2 tetrahedra,  an edgeedge with one O(2)MgV2Zn2 square pyramid, and edges with two equivalent O(1)MgVZn3 square pyramids.