MgV2Zn2O7 crystallizes in the monoclinic Cm space group. Mg(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(4) atoms to form VO5 trigonal bipyramids that share corners with four equivalent Zn(1)O6 pentagonal pyramids,  a cornercorner with one V(2)O5 trigonal bipyramid, edges with two equivalent Zn(1)O6 pentagonal pyramids, and  an edgeedge with one V(2)O5 trigonal bipyramid. In the second V site, V(2) is bonded to one O(1), one O(2), one O(5), and two equivalent O(3) atoms to form VO5 trigonal bipyramids that share corners with four equivalent Zn(1)O6 pentagonal pyramids,  a cornercorner with one V(1)O5 trigonal bipyramid, edges with two equivalent Zn(1)O6 pentagonal pyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. Zn(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted ZnO6 pentagonal pyramids that share corners with two equivalent V(1)O5 trigonal bipyramids, corners with two equivalent V(2)O5 trigonal bipyramids, edges with three equivalent Zn(1)O6 pentagonal pyramids,  an edgeedge with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(2)O5 trigonal bipyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(2), and two equivalent Zn(1) atoms to form OV2Zn2 trigonal pyramids that share corners with two equivalent O(3)MgVZn2 trigonal pyramids, edges with two equivalent O(2)MgV2Zn2 trigonal bipyramids, and edges with two equivalent O(3)MgVZn2 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1), one V(1), one V(2), and two equivalent Zn(1) atoms to form OMgV2Zn2 trigonal bipyramids that share corners with four equivalent O(3)MgVZn2 trigonal pyramids, edges with two equivalent O(3)MgVZn2 trigonal pyramids, and edges with two equivalent O(1)V2Zn2 trigonal pyramids. In the third O site, O(3) is bonded to one Mg(1), one V(2), and two equivalent Zn(1) atoms to form OMgVZn2 trigonal pyramids that share corners with two equivalent O(2)MgV2Zn2 trigonal bipyramids,  a cornercorner with one O(1)V2Zn2 trigonal pyramid, corners with two equivalent O(3)MgVZn2 trigonal pyramids,  an edgeedge with one O(2)MgV2Zn2 trigonal bipyramid,  an edgeedge with one O(3)MgVZn2 trigonal pyramid, and  an edgeedge with one O(1)V2Zn2 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Mg(1), one V(1), and two equivalent Zn(1) atoms. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one V(2) atom.
MgV2Zn2O7 crystallizes in the monoclinic Cm space group. Mg(1) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms. The Mg(1)-O(2) bond length is 2.11 Å. The Mg(1)-O(5) bond length is 2.05 Å. Both Mg(1)-O(3) bond lengths are 2.11 Å. Both Mg(1)-O(4) bond lengths are 2.34 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(4) atoms to form VO5 trigonal bipyramids that share corners with four equivalent Zn(1)O6 pentagonal pyramids,  a cornercorner with one V(2)O5 trigonal bipyramid, edges with two equivalent Zn(1)O6 pentagonal pyramids, and  an edgeedge with one V(2)O5 trigonal bipyramid. The V(1)-O(1) bond length is 1.85 Å. The V(1)-O(2) bond length is 2.08 Å. The V(1)-O(5) bond length is 1.87 Å. Both V(1)-O(4) bond lengths are 1.86 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(5), and two equivalent O(3) atoms to form VO5 trigonal bipyramids that share corners with four equivalent Zn(1)O6 pentagonal pyramids,  a cornercorner with one V(1)O5 trigonal bipyramid, edges with two equivalent Zn(1)O6 pentagonal pyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(2) bond length is 1.95 Å. The V(2)-O(5) bond length is 1.83 Å. Both V(2)-O(3) bond lengths are 1.85 Å. Zn(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted ZnO6 pentagonal pyramids that share corners with two equivalent V(1)O5 trigonal bipyramids, corners with two equivalent V(2)O5 trigonal bipyramids, edges with three equivalent Zn(1)O6 pentagonal pyramids,  an edgeedge with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(2)O5 trigonal bipyramid. The Zn(1)-O(1) bond length is 2.30 Å. The Zn(1)-O(2) bond length is 2.38 Å. There is one shorter (2.07 Å) and one longer (2.11 Å) Zn(1)-O(3) bond length. There is one shorter (2.05 Å) and one longer (2.22 Å) Zn(1)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(2), and two equivalent Zn(1) atoms to form OV2Zn2 trigonal pyramids that share corners with two equivalent O(3)MgVZn2 trigonal pyramids, edges with two equivalent O(2)MgV2Zn2 trigonal bipyramids, and edges with two equivalent O(3)MgVZn2 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1), one V(1), one V(2), and two equivalent Zn(1) atoms to form OMgV2Zn2 trigonal bipyramids that share corners with four equivalent O(3)MgVZn2 trigonal pyramids, edges with two equivalent O(3)MgVZn2 trigonal pyramids, and edges with two equivalent O(1)V2Zn2 trigonal pyramids. In the third O site, O(3) is bonded to one Mg(1), one V(2), and two equivalent Zn(1) atoms to form OMgVZn2 trigonal pyramids that share corners with two equivalent O(2)MgV2Zn2 trigonal bipyramids,  a cornercorner with one O(1)V2Zn2 trigonal pyramid, corners with two equivalent O(3)MgVZn2 trigonal pyramids,  an edgeedge with one O(2)MgV2Zn2 trigonal bipyramid,  an edgeedge with one O(3)MgVZn2 trigonal pyramid, and  an edgeedge with one O(1)V2Zn2 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted see-saw-like geometry to one Mg(1), one V(1), and two equivalent Zn(1) atoms. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one V(2) atom.