Li4Ti3Mn5O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and corners with four equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 51-54°. In the second Ti site, Ti(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Mn(4)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 50°. In the third Mn site, Mn(3) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), one Mn(1), and one Mn(4) atom. In the second O site, O(2) is bonded to one Li(4), two equivalent Ti(1), and one Mn(1) atom to form distorted OLiTi2Mn tetrahedra that share corners with two equivalent O(4)LiTi2Mn tetrahedra, corners with two equivalent O(6)LiTiMn2 tetrahedra, and edges with two equivalent O(6)LiTiMn2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one Mn(2) atom to form OLiTi2Mn tetrahedra that share corners with two equivalent O(2)LiTi2Mn tetrahedra and corners with four equivalent O(6)LiTiMn2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Ti(2), and two equivalent Mn(4) atoms to form distorted OLiTiMn2 tetrahedra that share corners with two equivalent O(12)LiMn3 tetrahedra and corners with four equivalent O(9)LiTiMn2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one Mn(1), and one Mn(2) atom to form distorted OLiTiMn2 tetrahedra that share  a cornercorner with one O(2)LiTi2Mn tetrahedra,  a cornercorner with one O(6)LiTiMn2 tetrahedra, corners with two equivalent O(4)LiTi2Mn tetrahedra,  an edgeedge with one O(2)LiTi2Mn tetrahedra, and  an edgeedge with one O(6)LiTiMn2 tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one Mn(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(1), and two equivalent Mn(4) atoms. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one Mn(3), and one Mn(4) atom to form distorted OLiTiMn2 tetrahedra that share  a cornercorner with one O(12)LiMn3 tetrahedra,  a cornercorner with one O(9)LiTiMn2 tetrahedra, corners with two equivalent O(5)LiTiMn2 tetrahedra,  an edgeedge with one O(12)LiMn3 tetrahedra, and  an edgeedge with one O(9)LiTiMn2 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(2), and two equivalent Mn(4) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Mn(2), and one Mn(3) atom. In the twelfth O site, O(12) is bonded to one Li(1), one Mn(3), and two equivalent Mn(4) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra.
Li4Ti3Mn5O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and corners with four equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. The Li(1)-O(12) bond length is 1.95 Å. The Li(1)-O(3) bond length is 2.08 Å. Both Li(1)-O(9) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. The Li(2)-O(5) bond length is 1.81 Å. The Li(2)-O(7) bond length is 1.95 Å. Both Li(2)-O(11) bond lengths are 1.96 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.82 Å. The Li(3)-O(8) bond length is 1.95 Å. Both Li(3)-O(1) bond lengths are 1.97 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(4)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. The Li(4)-O(10) bond length is 2.08 Å. The Li(4)-O(2) bond length is 1.97 Å. Both Li(4)-O(6) bond lengths are 1.96 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 51-54°. The Ti(1)-O(11) bond length is 2.03 Å. The Ti(1)-O(2) bond length is 2.01 Å. The Ti(1)-O(3) bond length is 2.01 Å. The Ti(1)-O(4) bond length is 2.00 Å. The Ti(1)-O(6) bond length is 1.88 Å. The Ti(1)-O(7) bond length is 1.97 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Ti(2)-O(10) bond length is 1.96 Å. The Ti(2)-O(5) bond length is 2.01 Å. Both Ti(2)-O(1) bond lengths are 1.96 Å. Both Ti(2)-O(9) bond lengths are 2.01 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Mn(4)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. The Mn(1)-O(2) bond length is 2.10 Å. The Mn(1)-O(8) bond length is 2.01 Å. Both Mn(1)-O(1) bond lengths are 2.17 Å. Both Mn(1)-O(6) bond lengths are 2.17 Å. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 50°. The Mn(2)-O(3) bond length is 1.93 Å. The Mn(2)-O(4) bond length is 1.92 Å. Both Mn(2)-O(11) bond lengths are 2.09 Å. Both Mn(2)-O(6) bond lengths are 2.11 Å. In the third Mn site, Mn(3) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 trigonal pyramids,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. The Mn(3)-O(12) bond length is 2.23 Å. The Mn(3)-O(7) bond length is 2.28 Å. Both Mn(3)-O(11) bond lengths are 1.98 Å. Both Mn(3)-O(9) bond lengths are 2.07 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Mn(4)-O(1) bond length is 1.97 Å. The Mn(4)-O(10) bond length is 2.00 Å. The Mn(4)-O(12) bond length is 1.96 Å. The Mn(4)-O(5) bond length is 1.95 Å. The Mn(4)-O(8) bond length is 2.02 Å. The Mn(4)-O(9) bond length is 2.00 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), one Mn(1), and one Mn(4) atom. In the second O site, O(2) is bonded to one Li(4), two equivalent Ti(1), and one Mn(1) atom to form distorted OLiTi2Mn tetrahedra that share corners with two equivalent O(4)LiTi2Mn tetrahedra, corners with two equivalent O(6)LiTiMn2 tetrahedra, and edges with two equivalent O(6)LiTiMn2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one Mn(2) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one Mn(2) atom to form OLiTi2Mn tetrahedra that share corners with two equivalent O(2)LiTi2Mn tetrahedra and corners with four equivalent O(6)LiTiMn2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Ti(2), and two equivalent Mn(4) atoms to form distorted OLiTiMn2 tetrahedra that share corners with two equivalent O(12)LiMn3 tetrahedra and corners with four equivalent O(9)LiTiMn2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one Mn(1), and one Mn(2) atom to form distorted OLiTiMn2 tetrahedra that share  a cornercorner with one O(2)LiTi2Mn tetrahedra,  a cornercorner with one O(6)LiTiMn2 tetrahedra, corners with two equivalent O(4)LiTi2Mn tetrahedra,  an edgeedge with one O(2)LiTi2Mn tetrahedra, and  an edgeedge with one O(6)LiTiMn2 tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one Mn(3) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one Mn(1), and two equivalent Mn(4) atoms. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one Mn(3), and one Mn(4) atom to form distorted OLiTiMn2 tetrahedra that share  a cornercorner with one O(12)LiMn3 tetrahedra,  a cornercorner with one O(9)LiTiMn2 tetrahedra, corners with two equivalent O(5)LiTiMn2 tetrahedra,  an edgeedge with one O(12)LiMn3 tetrahedra, and  an edgeedge with one O(9)LiTiMn2 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(2), and two equivalent Mn(4) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Mn(2), and one Mn(3) atom. In the twelfth O site, O(12) is bonded to one Li(1), one Mn(3), and two equivalent Mn(4) atoms to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra.