MgV2Zn2O7 crystallizes in the monoclinic C2 space group. Mg(1) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MgO5 trigonal bipyramids that share corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Zn(1)O6 octahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. V(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form VO5 trigonal bipyramids that share corners with two equivalent Zn(1)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid,  a cornercorner with one V(1)O5 trigonal bipyramid,  an edgeedge with one Zn(1)O6 octahedra,  an edgeedge with one Mg(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-57°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted ZnO6 octahedra that share corners with four equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. In the second Zn site, Zn(2) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(1), one Zn(1), and one Zn(2) atom to form distorted OV2Zn2 tetrahedra that share corners with four equivalent O(4)MgVZn2 tetrahedra,  an edgeedge with one O(4)MgVZn2 tetrahedra, and edges with two equivalent O(1)V2Zn2 tetrahedra. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one Zn(1) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Mg(1) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Mg(1), one V(1), one Zn(1), and one Zn(2) atom to form distorted OMgVZn2 tetrahedra that share corners with three equivalent O(4)MgVZn2 tetrahedra, corners with four equivalent O(1)V2Zn2 tetrahedra, and  an edgeedge with one O(1)V2Zn2 tetrahedra.
MgV2Zn2O7 crystallizes in the monoclinic C2 space group. Mg(1) is bonded to one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MgO5 trigonal bipyramids that share corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Zn(1)O6 octahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. The Mg(1)-O(3) bond length is 2.03 Å. Both Mg(1)-O(2) bond lengths are 2.06 Å. Both Mg(1)-O(4) bond lengths are 2.06 Å. V(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form VO5 trigonal bipyramids that share corners with two equivalent Zn(1)O6 octahedra,  a cornercorner with one Mg(1)O5 trigonal bipyramid,  a cornercorner with one V(1)O5 trigonal bipyramid,  an edgeedge with one Zn(1)O6 octahedra,  an edgeedge with one Mg(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-57°. The V(1)-O(2) bond length is 1.77 Å. The V(1)-O(3) bond length is 1.93 Å. The V(1)-O(4) bond length is 1.90 Å. There is one shorter (1.91 Å) and one longer (2.10 Å) V(1)-O(1) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted ZnO6 octahedra that share corners with four equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Mg(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. Both Zn(1)-O(1) bond lengths are 2.09 Å. Both Zn(1)-O(2) bond lengths are 2.07 Å. Both Zn(1)-O(4) bond lengths are 2.28 Å. In the second Zn site, Zn(2) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Zn(2)-O(1) bond lengths are 2.13 Å. Both Zn(2)-O(4) bond lengths are 2.01 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(1), one Zn(1), and one Zn(2) atom to form distorted OV2Zn2 tetrahedra that share corners with four equivalent O(4)MgVZn2 tetrahedra,  an edgeedge with one O(4)MgVZn2 tetrahedra, and edges with two equivalent O(1)V2Zn2 tetrahedra. In the second O site, O(2) is bonded in a T-shaped geometry to one Mg(1), one V(1), and one Zn(1) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Mg(1) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Mg(1), one V(1), one Zn(1), and one Zn(2) atom to form distorted OMgVZn2 tetrahedra that share corners with three equivalent O(4)MgVZn2 tetrahedra, corners with four equivalent O(1)V2Zn2 tetrahedra, and  an edgeedge with one O(1)V2Zn2 tetrahedra.