MgTi2O4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted MgO6 pentagonal pyramids that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Ti(2)O6 octahedra, and edges with two equivalent Mg(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-9°. In the second Mg site, Mg(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted MgO6 pentagonal pyramids that share corners with four equivalent Ti(1)O6 octahedra, corners with eight equivalent Ti(2)O6 octahedra, edges with two equivalent Mg(1)O6 pentagonal pyramids, and faces with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Mg(2)O6 pentagonal pyramids, corners with three equivalent Mg(1)O6 pentagonal pyramids, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Mg(1)O6 pentagonal pyramid, and  a faceface with one Mg(2)O6 pentagonal pyramid. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with four equivalent Mg(2)O6 pentagonal pyramids, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with two equivalent Mg(1)O6 pentagonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(2), one Ti(1), and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded to one Mg(1), one Mg(2), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing OMg2Ti3 trigonal bipyramids.
MgTi2O4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted MgO6 pentagonal pyramids that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Ti(2)O6 octahedra, and edges with two equivalent Mg(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-9°. Both Mg(1)-O(1) bond lengths are 2.05 Å. All Mg(1)-O(3) bond lengths are 2.20 Å. In the second Mg site, Mg(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form distorted MgO6 pentagonal pyramids that share corners with four equivalent Ti(1)O6 octahedra, corners with eight equivalent Ti(2)O6 octahedra, edges with two equivalent Mg(1)O6 pentagonal pyramids, and faces with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-54°. Both Mg(2)-O(2) bond lengths are 2.14 Å. All Mg(2)-O(3) bond lengths are 2.22 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Mg(2)O6 pentagonal pyramids, corners with three equivalent Mg(1)O6 pentagonal pyramids, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Mg(1)O6 pentagonal pyramid, and  a faceface with one Mg(2)O6 pentagonal pyramid. The Ti(1)-O(1) bond length is 1.99 Å. The Ti(1)-O(2) bond length is 2.10 Å. There are two shorter (2.07 Å) and two longer (2.09 Å) Ti(1)-O(3) bond lengths. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with four equivalent Mg(2)O6 pentagonal pyramids, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with two equivalent Mg(1)O6 pentagonal pyramids. Both Ti(2)-O(1) bond lengths are 2.03 Å. Both Ti(2)-O(2) bond lengths are 2.02 Å. Both Ti(2)-O(3) bond lengths are 2.10 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Mg(2), one Ti(1), and two equivalent Ti(2) atoms. In the third O site, O(3) is bonded to one Mg(1), one Mg(2), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing OMg2Ti3 trigonal bipyramids.