MgTi2Mn2O6 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form edge-sharing MgO6 octahedra. Ti(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(3), and three equivalent O(2) atoms. Mn(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), two equivalent Ti(1), and one Mn(1) atom to form distorted OMg2Ti2Mn trigonal bipyramids that share corners with five equivalent O(2)Ti3Mn tetrahedra, corners with two equivalent O(1)Mg2Ti2Mn trigonal bipyramids, corners with two equivalent O(3)MgTi2Mn2 trigonal bipyramids,  an edgeedge with one O(2)Ti3Mn tetrahedra, edges with three equivalent O(1)Mg2Ti2Mn trigonal bipyramids, and edges with four equivalent O(3)MgTi2Mn2 trigonal bipyramids. In the second O site, O(2) is bonded to three equivalent Ti(1) and one Mn(1) atom to form distorted OTi3Mn tetrahedra that share corners with two equivalent O(2)Ti3Mn tetrahedra, corners with four equivalent O(3)MgTi2Mn2 trigonal bipyramids, corners with five equivalent O(1)Mg2Ti2Mn trigonal bipyramids, edges with two equivalent O(2)Ti3Mn tetrahedra,  an edgeedge with one O(1)Mg2Ti2Mn trigonal bipyramid, and edges with two equivalent O(3)MgTi2Mn2 trigonal bipyramids. In the third O site, O(3) is bonded to one Mg(1), two equivalent Ti(1), and two equivalent Mn(1) atoms to form OMgTi2Mn2 trigonal bipyramids that share corners with four equivalent O(2)Ti3Mn tetrahedra, corners with two equivalent O(1)Mg2Ti2Mn trigonal bipyramids, corners with three equivalent O(3)MgTi2Mn2 trigonal bipyramids, edges with two equivalent O(2)Ti3Mn tetrahedra,  an edgeedge with one O(3)MgTi2Mn2 trigonal bipyramid, and edges with four equivalent O(1)Mg2Ti2Mn trigonal bipyramids.
MgTi2Mn2O6 crystallizes in the monoclinic C2/m space group. Mg(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form edge-sharing MgO6 octahedra. Both Mg(1)-O(3) bond lengths are 2.09 Å. All Mg(1)-O(1) bond lengths are 2.12 Å. Ti(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(3), and three equivalent O(2) atoms. Both Ti(1)-O(1) bond lengths are 2.21 Å. There is one shorter (2.10 Å) and one longer (2.23 Å) Ti(1)-O(3) bond length. There are two shorter (1.99 Å) and one longer (2.33 Å) Ti(1)-O(2) bond length. Mn(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(3) atoms. The Mn(1)-O(1) bond length is 2.10 Å. The Mn(1)-O(2) bond length is 2.00 Å. Both Mn(1)-O(3) bond lengths are 2.20 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), two equivalent Ti(1), and one Mn(1) atom to form distorted OMg2Ti2Mn trigonal bipyramids that share corners with five equivalent O(2)Ti3Mn tetrahedra, corners with two equivalent O(1)Mg2Ti2Mn trigonal bipyramids, corners with two equivalent O(3)MgTi2Mn2 trigonal bipyramids,  an edgeedge with one O(2)Ti3Mn tetrahedra, edges with three equivalent O(1)Mg2Ti2Mn trigonal bipyramids, and edges with four equivalent O(3)MgTi2Mn2 trigonal bipyramids. In the second O site, O(2) is bonded to three equivalent Ti(1) and one Mn(1) atom to form distorted OTi3Mn tetrahedra that share corners with two equivalent O(2)Ti3Mn tetrahedra, corners with four equivalent O(3)MgTi2Mn2 trigonal bipyramids, corners with five equivalent O(1)Mg2Ti2Mn trigonal bipyramids, edges with two equivalent O(2)Ti3Mn tetrahedra,  an edgeedge with one O(1)Mg2Ti2Mn trigonal bipyramid, and edges with two equivalent O(3)MgTi2Mn2 trigonal bipyramids. In the third O site, O(3) is bonded to one Mg(1), two equivalent Ti(1), and two equivalent Mn(1) atoms to form OMgTi2Mn2 trigonal bipyramids that share corners with four equivalent O(2)Ti3Mn tetrahedra, corners with two equivalent O(1)Mg2Ti2Mn trigonal bipyramids, corners with three equivalent O(3)MgTi2Mn2 trigonal bipyramids, edges with two equivalent O(2)Ti3Mn tetrahedra,  an edgeedge with one O(3)MgTi2Mn2 trigonal bipyramid, and edges with four equivalent O(1)Mg2Ti2Mn trigonal bipyramids.