Li2TiMn3O8 is Hausmannite-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and corners with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. In the second Li site, Li(2) is bonded to one O(4), one O(6), and two equivalent O(1) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Ti(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-67°. Ti(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. There are six inequivalent O sites. In the first O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), and two equivalent Mn(1) atoms. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Mn(1), and one Mn(2) atom. In the third O site, O(2) is bonded to one Li(1), one Ti(1), and two equivalent Mn(1) atoms to form distorted OLiTiMn2 tetrahedra that share corners with two equivalent O(4)LiMn3 tetrahedra, corners with two equivalent O(5)LiTiMn2 trigonal pyramids, and edges with two equivalent O(5)LiTiMn2 trigonal pyramids. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(1) atoms. In the fifth O site, O(4) is bonded to one Li(2), one Mn(2), and two equivalent Mn(1) atoms to form corner-sharing OLiMn3 tetrahedra. In the sixth O site, O(5) is bonded to one Li(1), one Ti(1), one Mn(1), and one Mn(2) atom to form distorted OLiTiMn2 trigonal pyramids that share  a cornercorner with one O(2)LiTiMn2 tetrahedra, corners with two equivalent O(4)LiMn3 tetrahedra,  a cornercorner with one O(5)LiTiMn2 trigonal pyramid,  an edgeedge with one O(2)LiTiMn2 tetrahedra, and  an edgeedge with one O(5)LiTiMn2 trigonal pyramid.
Li2TiMn3O8 is Hausmannite-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and corners with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.06 Å. Both Li(1)-O(5) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to one O(4), one O(6), and two equivalent O(1) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with three equivalent Ti(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-67°. The Li(2)-O(4) bond length is 1.82 Å. The Li(2)-O(6) bond length is 1.98 Å. Both Li(2)-O(1) bond lengths are 1.97 Å. Ti(1) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Ti(1)-O(2) bond length is 2.16 Å. The Ti(1)-O(6) bond length is 1.99 Å. Both Ti(1)-O(1) bond lengths are 1.91 Å. Both Ti(1)-O(5) bond lengths are 2.05 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted MnO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. The Mn(1)-O(1) bond length is 2.32 Å. The Mn(1)-O(2) bond length is 1.96 Å. The Mn(1)-O(3) bond length is 1.95 Å. The Mn(1)-O(4) bond length is 1.95 Å. The Mn(1)-O(5) bond length is 2.20 Å. The Mn(1)-O(6) bond length is 2.00 Å. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 47°. The Mn(2)-O(3) bond length is 1.93 Å. The Mn(2)-O(4) bond length is 1.94 Å. Both Mn(2)-O(1) bond lengths are 2.00 Å. Both Mn(2)-O(5) bond lengths are 1.90 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), and two equivalent Mn(1) atoms. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Mn(1), and one Mn(2) atom. In the third O site, O(2) is bonded to one Li(1), one Ti(1), and two equivalent Mn(1) atoms to form distorted OLiTiMn2 tetrahedra that share corners with two equivalent O(4)LiMn3 tetrahedra, corners with two equivalent O(5)LiTiMn2 trigonal pyramids, and edges with two equivalent O(5)LiTiMn2 trigonal pyramids. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(1) atoms. In the fifth O site, O(4) is bonded to one Li(2), one Mn(2), and two equivalent Mn(1) atoms to form corner-sharing OLiMn3 tetrahedra. In the sixth O site, O(5) is bonded to one Li(1), one Ti(1), one Mn(1), and one Mn(2) atom to form distorted OLiTiMn2 trigonal pyramids that share  a cornercorner with one O(2)LiTiMn2 tetrahedra, corners with two equivalent O(4)LiMn3 tetrahedra,  a cornercorner with one O(5)LiTiMn2 trigonal pyramid,  an edgeedge with one O(2)LiTiMn2 tetrahedra, and  an edgeedge with one O(5)LiTiMn2 trigonal pyramid.