MgTi2V2O8 crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one O(5), one O(6), two equivalent O(3), and two equivalent O(4) atoms to form distorted MgO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O4 tetrahedra, corners with two equivalent Ti(1)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O5 trigonal bipyramid, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 66°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted TiO5 trigonal bipyramids that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 69°. In the second Ti site, Ti(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(6), 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(5), two equivalent O(3), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Ti(1)O5 trigonal bipyramids, and  a faceface with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles are 66°. In the second V site, V(2) is bonded to one O(5), one O(6), and two equivalent O(3) atoms to form distorted VO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Mg(1)O6 octahedra, and corners with two equivalent Ti(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-72°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(2) and one V(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one Ti(2) atom. In the third O site, O(3) is bonded to one Mg(1), one Ti(1), one V(1), and one V(2) atom to form a mixture of distorted face and corner-sharing OMgTiV2 tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Mg(1), one Ti(1), one Ti(2), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mg(1), one Ti(2), and one V(2) atom.
MgTi2V2O8 crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one O(5), one O(6), two equivalent O(3), and two equivalent O(4) atoms to form distorted MgO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(2)O4 tetrahedra, corners with two equivalent Ti(1)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O5 trigonal bipyramid, and  a faceface with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 66°. The Mg(1)-O(5) bond length is 2.00 Å. The Mg(1)-O(6) bond length is 1.97 Å. Both Mg(1)-O(3) bond lengths are 2.15 Å. Both Mg(1)-O(4) bond lengths are 2.44 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted TiO5 trigonal bipyramids that share corners with two equivalent Mg(1)O6 octahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Mg(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 69°. The Ti(1)-O(2) bond length is 1.79 Å. Both Ti(1)-O(3) bond lengths are 2.00 Å. Both Ti(1)-O(4) bond lengths are 1.93 Å. In the second Ti site, Ti(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(6), and two equivalent O(4) atoms. The Ti(2)-O(1) bond length is 1.72 Å. The Ti(2)-O(2) bond length is 1.89 Å. The Ti(2)-O(6) bond length is 2.32 Å. Both Ti(2)-O(4) bond lengths are 1.93 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(5), two equivalent O(3), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent Mg(1)O6 octahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Ti(1)O5 trigonal bipyramids, and  a faceface with one Mg(1)O6 octahedra. The corner-sharing octahedral tilt angles are 66°. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(5) bond length is 2.14 Å. Both V(1)-O(3) bond lengths are 2.36 Å. Both V(1)-O(4) bond lengths are 2.23 Å. In the second V site, V(2) is bonded to one O(5), one O(6), and two equivalent O(3) atoms to form distorted VO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Mg(1)O6 octahedra, and corners with two equivalent Ti(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-72°. The V(2)-O(5) bond length is 1.81 Å. The V(2)-O(6) bond length is 1.76 Å. Both V(2)-O(3) bond lengths are 1.91 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(2) and one V(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one Ti(2) atom. In the third O site, O(3) is bonded to one Mg(1), one Ti(1), one V(1), and one V(2) atom to form a mixture of distorted face and corner-sharing OMgTiV2 tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Mg(1), one Ti(1), one Ti(2), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Mg(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Mg(1), one Ti(2), and one V(2) atom.