MgTi2O4 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form MgO5 square pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with two equivalent Mg(1)O5 square pyramids, and  a faceface with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-57°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form distorted TiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra, corners with two equivalent Mg(1)O5 square pyramids, edges with four equivalent Ti(1)O6 octahedra, and edges with three equivalent Mg(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 47-49°. In the second Ti site, Ti(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form TiO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra, corners with four equivalent Mg(1)O5 square pyramids, edges with four equivalent Ti(2)O6 octahedra, and  a faceface with one Mg(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 47-49°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one Ti(2), and two equivalent Ti(1) atoms to form OMgTi3 trigonal pyramids that share corners with two equivalent O(3)Mg2Ti3 square pyramids,  a cornercorner with one O(4)Mg2Ti3 trigonal bipyramid, corners with two equivalent O(1)MgTi3 trigonal pyramids, edges with three equivalent O(3)Mg2Ti3 square pyramids, and edges with two equivalent O(4)Mg2Ti3 trigonal bipyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded to two equivalent Mg(1) and three equivalent Ti(1) atoms to form OMg2Ti3 square pyramids that share corners with two equivalent O(4)Mg2Ti3 trigonal bipyramids, corners with two equivalent O(1)MgTi3 trigonal pyramids, edges with four equivalent O(3)Mg2Ti3 square pyramids,  an edgeedge with one O(4)Mg2Ti3 trigonal bipyramid, and edges with three equivalent O(1)MgTi3 trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Mg(1) and three equivalent Ti(2) atoms to form distorted OMg2Ti3 trigonal bipyramids that share corners with two equivalent O(3)Mg2Ti3 square pyramids,  a cornercorner with one O(1)MgTi3 trigonal pyramid,  an edgeedge with one O(3)Mg2Ti3 square pyramid, edges with four equivalent O(4)Mg2Ti3 trigonal bipyramids, and edges with two equivalent O(1)MgTi3 trigonal pyramids.
MgTi2O4 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form MgO5 square pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with two equivalent Mg(1)O5 square pyramids, and  a faceface with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-57°. The Mg(1)-O(1) bond length is 2.14 Å. Both Mg(1)-O(3) bond lengths are 2.08 Å. Both Mg(1)-O(4) bond lengths are 2.12 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form distorted TiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra, corners with two equivalent Mg(1)O5 square pyramids, edges with four equivalent Ti(1)O6 octahedra, and edges with three equivalent Mg(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 47-49°. The Ti(1)-O(2) bond length is 1.89 Å. Both Ti(1)-O(1) bond lengths are 2.01 Å. There are two shorter (2.09 Å) and one longer (2.35 Å) Ti(1)-O(3) bond length. In the second Ti site, Ti(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form TiO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra, corners with four equivalent Mg(1)O5 square pyramids, edges with four equivalent Ti(2)O6 octahedra, and  a faceface with one Mg(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 47-49°. The Ti(2)-O(1) bond length is 2.01 Å. Both Ti(2)-O(2) bond lengths are 2.00 Å. There is one shorter (2.02 Å) and two longer (2.20 Å) Ti(2)-O(4) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one Ti(2), and two equivalent Ti(1) atoms to form OMgTi3 trigonal pyramids that share corners with two equivalent O(3)Mg2Ti3 square pyramids,  a cornercorner with one O(4)Mg2Ti3 trigonal bipyramid, corners with two equivalent O(1)MgTi3 trigonal pyramids, edges with three equivalent O(3)Mg2Ti3 square pyramids, and edges with two equivalent O(4)Mg2Ti3 trigonal bipyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded to two equivalent Mg(1) and three equivalent Ti(1) atoms to form OMg2Ti3 square pyramids that share corners with two equivalent O(4)Mg2Ti3 trigonal bipyramids, corners with two equivalent O(1)MgTi3 trigonal pyramids, edges with four equivalent O(3)Mg2Ti3 square pyramids,  an edgeedge with one O(4)Mg2Ti3 trigonal bipyramid, and edges with three equivalent O(1)MgTi3 trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Mg(1) and three equivalent Ti(2) atoms to form distorted OMg2Ti3 trigonal bipyramids that share corners with two equivalent O(3)Mg2Ti3 square pyramids,  a cornercorner with one O(1)MgTi3 trigonal pyramid,  an edgeedge with one O(3)Mg2Ti3 square pyramid, edges with four equivalent O(4)Mg2Ti3 trigonal bipyramids, and edges with two equivalent O(1)MgTi3 trigonal pyramids.