MgTi4O6 crystallizes in the orthorhombic Cmcm space group. Mg(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. 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 a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ti(2) and four equivalent Ti(1) atoms to form OTi6 octahedra that share corners with four equivalent O(3)MgTi5 octahedra, corners with two equivalent O(4)Mg2Ti2 tetrahedra, edges with two equivalent O(1)Ti6 octahedra, edges with six equivalent O(3)MgTi5 octahedra, and edges with four equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. In the second O site, O(2) is bonded to two equivalent Mg(1), one Ti(1), and two equivalent Ti(2) atoms to form distorted OMg2Ti3 trigonal bipyramids that share corners with five equivalent O(3)MgTi5 octahedra, corners with four equivalent O(4)Mg2Ti2 tetrahedra, corners with two equivalent O(2)Mg2Ti3 trigonal bipyramids, edges with two equivalent O(1)Ti6 octahedra, edges with three equivalent O(3)MgTi5 octahedra,  an edgeedge with one O(4)Mg2Ti2 tetrahedra, and edges with three equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-43°. In the third O site, O(3) is bonded to one Mg(1), two equivalent Ti(2), and three equivalent Ti(1) atoms to form distorted OMgTi5 octahedra that share  a cornercorner with one O(3)MgTi5 octahedra, corners with two equivalent O(1)Ti6 octahedra, corners with five equivalent O(2)Mg2Ti3 trigonal bipyramids, edges with three equivalent O(1)Ti6 octahedra, edges with four equivalent O(3)MgTi5 octahedra, edges with two equivalent O(4)Mg2Ti2 tetrahedra, and edges with three equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-49°. In the fourth O site, O(4) is bonded to two equivalent Mg(1) and two equivalent Ti(2) atoms to form OMg2Ti2 tetrahedra that share corners with two equivalent O(1)Ti6 octahedra, corners with two equivalent O(4)Mg2Ti2 tetrahedra, corners with eight equivalent O(2)Mg2Ti3 trigonal bipyramids, edges with four equivalent O(3)MgTi5 octahedra, and edges with two equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedra are not tilted.
MgTi4O6 crystallizes in the orthorhombic Cmcm space group. Mg(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(2) atoms. Both Mg(1)-O(3) bond lengths are 2.54 Å. Both Mg(1)-O(4) bond lengths are 2.11 Å. All Mg(1)-O(2) bond lengths are 2.27 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 a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Ti(1)-O(2) bond length is 2.09 Å. Both Ti(1)-O(1) bond lengths are 2.15 Å. There are two shorter (2.06 Å) and one longer (2.21 Å) Ti(1)-O(3) bond length. In the second Ti site, Ti(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. The Ti(2)-O(1) bond length is 2.18 Å. The Ti(2)-O(4) bond length is 2.01 Å. Both Ti(2)-O(2) bond lengths are 2.09 Å. Both Ti(2)-O(3) bond lengths are 2.07 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ti(2) and four equivalent Ti(1) atoms to form OTi6 octahedra that share corners with four equivalent O(3)MgTi5 octahedra, corners with two equivalent O(4)Mg2Ti2 tetrahedra, edges with two equivalent O(1)Ti6 octahedra, edges with six equivalent O(3)MgTi5 octahedra, and edges with four equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 10°. In the second O site, O(2) is bonded to two equivalent Mg(1), one Ti(1), and two equivalent Ti(2) atoms to form distorted OMg2Ti3 trigonal bipyramids that share corners with five equivalent O(3)MgTi5 octahedra, corners with four equivalent O(4)Mg2Ti2 tetrahedra, corners with two equivalent O(2)Mg2Ti3 trigonal bipyramids, edges with two equivalent O(1)Ti6 octahedra, edges with three equivalent O(3)MgTi5 octahedra,  an edgeedge with one O(4)Mg2Ti2 tetrahedra, and edges with three equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-43°. In the third O site, O(3) is bonded to one Mg(1), two equivalent Ti(2), and three equivalent Ti(1) atoms to form distorted OMgTi5 octahedra that share  a cornercorner with one O(3)MgTi5 octahedra, corners with two equivalent O(1)Ti6 octahedra, corners with five equivalent O(2)Mg2Ti3 trigonal bipyramids, edges with three equivalent O(1)Ti6 octahedra, edges with four equivalent O(3)MgTi5 octahedra, edges with two equivalent O(4)Mg2Ti2 tetrahedra, and edges with three equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-49°. In the fourth O site, O(4) is bonded to two equivalent Mg(1) and two equivalent Ti(2) atoms to form OMg2Ti2 tetrahedra that share corners with two equivalent O(1)Ti6 octahedra, corners with two equivalent O(4)Mg2Ti2 tetrahedra, corners with eight equivalent O(2)Mg2Ti3 trigonal bipyramids, edges with four equivalent O(3)MgTi5 octahedra, and edges with two equivalent O(2)Mg2Ti3 trigonal bipyramids. The corner-sharing octahedra are not tilted.