MgTi2(CoO2)4 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MgO6 octahedra that share corners with six equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), and two equivalent O(2) atoms. In the second Co site, Co(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Mg(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. In the third Co site, Co(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), two equivalent Ti(1), one Co(1), and one Co(2) atom to form OMgTi2Co2 trigonal bipyramids that share corners with three equivalent O(3)Ti2Co2 tetrahedra, corners with two equivalent O(2)MgTiCo3 trigonal bipyramids, corners with four equivalent O(1)MgTi2Co2 trigonal bipyramids,  an edgeedge with one O(3)Ti2Co2 tetrahedra, and edges with six equivalent O(2)MgTiCo3 trigonal bipyramids. In the second O site, O(2) is bonded to one Mg(1), one Ti(1), one Co(1), one Co(2), and one Co(3) atom to form OMgTiCo3 trigonal bipyramids that share corners with three equivalent O(3)Ti2Co2 tetrahedra,  a cornercorner with one O(1)MgTi2Co2 trigonal bipyramid, corners with five equivalent O(2)MgTiCo3 trigonal bipyramids,  an edgeedge with one O(3)Ti2Co2 tetrahedra, edges with three equivalent O(1)MgTi2Co2 trigonal bipyramids, and edges with three equivalent O(2)MgTiCo3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Ti(1), one Co(1), and one Co(3) atom to form distorted OTi2Co2 tetrahedra that share corners with three equivalent O(3)Ti2Co2 tetrahedra, corners with three equivalent O(1)MgTi2Co2 trigonal bipyramids, corners with six equivalent O(2)MgTiCo3 trigonal bipyramids,  an edgeedge with one O(1)MgTi2Co2 trigonal bipyramid, and edges with two equivalent O(2)MgTiCo3 trigonal bipyramids.
MgTi2(CoO2)4 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MgO6 octahedra that share corners with six equivalent Co(2)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. Both Mg(1)-O(1) bond lengths are 2.09 Å. All Mg(1)-O(2) bond lengths are 2.13 Å. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. Both Ti(1)-O(1) bond lengths are 2.06 Å. Both Ti(1)-O(2) bond lengths are 2.01 Å. Both Ti(1)-O(3) bond lengths are 1.97 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Co(1)-O(1) bond length is 2.24 Å. The Co(1)-O(3) bond length is 1.87 Å. Both Co(1)-O(2) bond lengths are 2.15 Å. In the second Co site, Co(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Mg(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. Both Co(2)-O(1) bond lengths are 2.31 Å. All Co(2)-O(2) bond lengths are 2.23 Å. In the third Co site, Co(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share edges with two equivalent Mg(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Co(3)-O(3) bond lengths are 2.04 Å. All Co(3)-O(2) bond lengths are 2.14 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), two equivalent Ti(1), one Co(1), and one Co(2) atom to form OMgTi2Co2 trigonal bipyramids that share corners with three equivalent O(3)Ti2Co2 tetrahedra, corners with two equivalent O(2)MgTiCo3 trigonal bipyramids, corners with four equivalent O(1)MgTi2Co2 trigonal bipyramids,  an edgeedge with one O(3)Ti2Co2 tetrahedra, and edges with six equivalent O(2)MgTiCo3 trigonal bipyramids. In the second O site, O(2) is bonded to one Mg(1), one Ti(1), one Co(1), one Co(2), and one Co(3) atom to form OMgTiCo3 trigonal bipyramids that share corners with three equivalent O(3)Ti2Co2 tetrahedra,  a cornercorner with one O(1)MgTi2Co2 trigonal bipyramid, corners with five equivalent O(2)MgTiCo3 trigonal bipyramids,  an edgeedge with one O(3)Ti2Co2 tetrahedra, edges with three equivalent O(1)MgTi2Co2 trigonal bipyramids, and edges with three equivalent O(2)MgTiCo3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Ti(1), one Co(1), and one Co(3) atom to form distorted OTi2Co2 tetrahedra that share corners with three equivalent O(3)Ti2Co2 tetrahedra, corners with three equivalent O(1)MgTi2Co2 trigonal bipyramids, corners with six equivalent O(2)MgTiCo3 trigonal bipyramids,  an edgeedge with one O(1)MgTi2Co2 trigonal bipyramid, and edges with two equivalent O(2)MgTiCo3 trigonal bipyramids.