Li5Ti12O24 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(14), one O(2), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(15), one O(4), and two equivalent O(13) atoms. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(6), one O(9), and two equivalent O(12) atoms. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(10), one O(11), one O(12), and one O(5) atom. There are eight inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(14), one O(8), two equivalent O(16), 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 48-52°. In the second Ti site, Ti(2) is bonded to one O(13), one O(15), one O(16), one O(3), one O(4), and one O(7) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. In the third Ti site, Ti(3) is bonded to one O(1), one O(10), one O(12), one O(5), one O(6), and one O(9) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. In the fourth Ti site, Ti(4) is bonded to one O(11), one O(2), two equivalent O(10), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. In the fifth Ti site, Ti(5) is bonded to one O(11), one O(12), one O(16), one O(5), one O(7), and one O(8) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. In the sixth Ti site, Ti(6) is bonded to one O(15), one O(6), two equivalent O(12), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-49°. In the seventh Ti site, Ti(7) is bonded to one O(4), one O(9), two equivalent O(1), and two equivalent O(13) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the eighth Ti site, Ti(8) is bonded to one O(1), one O(10), one O(13), one O(14), one O(2), and one O(3) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(7), and one Ti(8) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(4), and two equivalent Ti(8) atoms. In the third O site, O(3) is bonded in a see-saw-like geometry to one Li(1), one Ti(1), one Ti(2), and one Ti(8) atom. In the fourth O site, O(4) is bonded in a tetrahedral geometry to one Li(2), one Ti(7), and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to one Li(4), one Ti(3), one Ti(4), and one Ti(5) atom to form distorted OLiTi3 tetrahedra that share  a cornercorner with one O(11)Li2Ti3 square pyramid,  a cornercorner with one O(12)Li2Ti3 square pyramid,  a cornercorner with one O(5)LiTi3 tetrahedra,  a cornercorner with one O(6)LiTi3 tetrahedra,  an edgeedge with one O(11)Li2Ti3 square pyramid, and  an edgeedge with one O(12)Li2Ti3 square pyramid. In the sixth O site, O(6) is bonded to one Li(3), one Ti(6), and two equivalent Ti(3) atoms to form distorted OLiTi3 tetrahedra that share corners with two equivalent O(12)Li2Ti3 square pyramids, corners with two equivalent O(5)LiTi3 tetrahedra, and edges with two equivalent O(12)Li2Ti3 square pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ti(2), one Ti(5), and one Ti(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ti(5) atoms. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(7), and two equivalent Ti(3) atoms. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(3), one Ti(4), and one Ti(8) atom. In the eleventh O site, O(11) is bonded to two equivalent Li(4), one Ti(4), and two equivalent Ti(5) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(5)LiTi3 tetrahedra, edges with two equivalent O(12)Li2Ti3 square pyramids, and edges with two equivalent O(5)LiTi3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(3), one Li(4), one Ti(3), one Ti(5), and one Ti(6) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(5)LiTi3 tetrahedra,  a cornercorner with one O(6)LiTi3 tetrahedra,  an edgeedge with one O(11)Li2Ti3 square pyramid,  an edgeedge with one O(12)Li2Ti3 square pyramid,  an edgeedge with one O(5)LiTi3 tetrahedra, and  an edgeedge with one O(6)LiTi3 tetrahedra. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(2), one Ti(7), and one Ti(8) atom. In the fourteenth O site, O(14) is bonded in a distorted tetrahedral geometry to one Li(1), one Ti(1), and two equivalent Ti(8) atoms. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(6), and two equivalent Ti(2) atoms. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(2), and one Ti(5) atom.
Li5Ti12O24 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(14), one O(2), and two equivalent O(3) atoms. The Li(1)-O(14) bond length is 1.87 Å. The Li(1)-O(2) bond length is 2.09 Å. Both Li(1)-O(3) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(15), one O(4), and two equivalent O(13) atoms. The Li(2)-O(15) bond length is 2.08 Å. The Li(2)-O(4) bond length is 1.87 Å. Both Li(2)-O(13) bond lengths are 1.99 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(6), one O(9), and two equivalent O(12) atoms. The Li(3)-O(6) bond length is 1.86 Å. The Li(3)-O(9) bond length is 2.10 Å. Both Li(3)-O(12) bond lengths are 2.00 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(10), one O(11), one O(12), and one O(5) atom. The Li(4)-O(10) bond length is 2.09 Å. The Li(4)-O(11) bond length is 1.99 Å. The Li(4)-O(12) bond length is 1.99 Å. The Li(4)-O(5) bond length is 1.88 Å. There are eight inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(14), one O(8), two equivalent O(16), 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 48-52°. The Ti(1)-O(14) bond length is 2.06 Å. The Ti(1)-O(8) bond length is 1.98 Å. Both Ti(1)-O(16) bond lengths are 1.99 Å. Both Ti(1)-O(3) bond lengths are 2.05 Å. In the second Ti site, Ti(2) is bonded to one O(13), one O(15), one O(16), one O(3), one O(4), and one O(7) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The Ti(2)-O(13) bond length is 2.07 Å. The Ti(2)-O(15) bond length is 2.07 Å. The Ti(2)-O(16) bond length is 1.98 Å. The Ti(2)-O(3) bond length is 1.97 Å. The Ti(2)-O(4) bond length is 2.04 Å. The Ti(2)-O(7) bond length is 1.95 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(10), one O(12), one O(5), one O(6), and one O(9) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. The Ti(3)-O(1) bond length is 1.94 Å. The Ti(3)-O(10) bond length is 2.05 Å. The Ti(3)-O(12) bond length is 2.07 Å. The Ti(3)-O(5) bond length is 2.04 Å. The Ti(3)-O(6) bond length is 2.00 Å. The Ti(3)-O(9) bond length is 2.02 Å. In the fourth Ti site, Ti(4) is bonded to one O(11), one O(2), two equivalent O(10), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. The Ti(4)-O(11) bond length is 2.11 Å. The Ti(4)-O(2) bond length is 1.93 Å. Both Ti(4)-O(10) bond lengths are 2.02 Å. Both Ti(4)-O(5) bond lengths are 2.01 Å. In the fifth Ti site, Ti(5) is bonded to one O(11), one O(12), one O(16), one O(5), one O(7), and one O(8) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 43-52°. The Ti(5)-O(11) bond length is 2.05 Å. The Ti(5)-O(12) bond length is 2.09 Å. The Ti(5)-O(16) bond length is 1.96 Å. The Ti(5)-O(5) bond length is 2.02 Å. The Ti(5)-O(7) bond length is 2.01 Å. The Ti(5)-O(8) bond length is 1.98 Å. In the sixth Ti site, Ti(6) is bonded to one O(15), one O(6), two equivalent O(12), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-49°. The Ti(6)-O(15) bond length is 1.96 Å. The Ti(6)-O(6) bond length is 2.05 Å. Both Ti(6)-O(12) bond lengths are 2.05 Å. Both Ti(6)-O(7) bond lengths are 1.99 Å. In the seventh Ti site, Ti(7) is bonded to one O(4), one O(9), two equivalent O(1), and two equivalent O(13) atoms to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Ti(7)-O(4) bond length is 2.00 Å. The Ti(7)-O(9) bond length is 2.01 Å. Both Ti(7)-O(1) bond lengths are 2.01 Å. Both Ti(7)-O(13) bond lengths are 2.04 Å. In the eighth Ti site, Ti(8) is bonded to one O(1), one O(10), one O(13), one O(14), one O(2), and one O(3) atom to form a mixture of corner and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 41-53°. The Ti(8)-O(1) bond length is 1.99 Å. The Ti(8)-O(10) bond length is 1.98 Å. The Ti(8)-O(13) bond length is 1.95 Å. The Ti(8)-O(14) bond length is 2.02 Å. The Ti(8)-O(2) bond length is 2.11 Å. The Ti(8)-O(3) bond length is 2.02 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(7), and one Ti(8) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(4), and two equivalent Ti(8) atoms. In the third O site, O(3) is bonded in a see-saw-like geometry to one Li(1), one Ti(1), one Ti(2), and one Ti(8) atom. In the fourth O site, O(4) is bonded in a tetrahedral geometry to one Li(2), one Ti(7), and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to one Li(4), one Ti(3), one Ti(4), and one Ti(5) atom to form distorted OLiTi3 tetrahedra that share  a cornercorner with one O(11)Li2Ti3 square pyramid,  a cornercorner with one O(12)Li2Ti3 square pyramid,  a cornercorner with one O(5)LiTi3 tetrahedra,  a cornercorner with one O(6)LiTi3 tetrahedra,  an edgeedge with one O(11)Li2Ti3 square pyramid, and  an edgeedge with one O(12)Li2Ti3 square pyramid. In the sixth O site, O(6) is bonded to one Li(3), one Ti(6), and two equivalent Ti(3) atoms to form distorted OLiTi3 tetrahedra that share corners with two equivalent O(12)Li2Ti3 square pyramids, corners with two equivalent O(5)LiTi3 tetrahedra, and edges with two equivalent O(12)Li2Ti3 square pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ti(2), one Ti(5), and one Ti(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ti(5) atoms. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(7), and two equivalent Ti(3) atoms. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(3), one Ti(4), and one Ti(8) atom. In the eleventh O site, O(11) is bonded to two equivalent Li(4), one Ti(4), and two equivalent Ti(5) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(5)LiTi3 tetrahedra, edges with two equivalent O(12)Li2Ti3 square pyramids, and edges with two equivalent O(5)LiTi3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(3), one Li(4), one Ti(3), one Ti(5), and one Ti(6) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(5)LiTi3 tetrahedra,  a cornercorner with one O(6)LiTi3 tetrahedra,  an edgeedge with one O(11)Li2Ti3 square pyramid,  an edgeedge with one O(12)Li2Ti3 square pyramid,  an edgeedge with one O(5)LiTi3 tetrahedra, and  an edgeedge with one O(6)LiTi3 tetrahedra. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(2), one Ti(7), and one Ti(8) atom. In the fourteenth O site, O(14) is bonded in a distorted tetrahedral geometry to one Li(1), one Ti(1), and two equivalent Ti(8) atoms. In the fifteenth O site, O(15) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(6), and two equivalent Ti(2) atoms. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(2), and one Ti(5) atom.