Li3Ti4O8 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO6 octahedra that share corners with three equivalent Ti(3)O6 octahedra, corners with four equivalent Li(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-54°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-50°. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(4)O6 octahedra, corners with three equivalent Li(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. In the third Ti site, Ti(3) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with four equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. In the fourth Ti site, Ti(4) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra, corners with four equivalent Ti(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-54°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Ti(1), one Ti(2), and one Ti(4) atom to form distorted OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(6)Li3Ti3 octahedra,  a cornercorner with one O(7)Li2Ti3 square pyramid, corners with two equivalent O(5)Li2Ti3 square pyramids, corners with two equivalent O(8)Li2Ti3 square pyramids,  a cornercorner with one O(3)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid,  an edgeedge with one O(6)Li3Ti3 octahedra,  an edgeedge with one O(5)Li2Ti3 square pyramid,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 6-7°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Ti(1), one Ti(2), and one Ti(3) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ti(2), one Ti(3), and one Ti(4) atom to form distorted OLi2Ti3 trigonal bipyramids that share  a cornercorner with one O(6)Li3Ti3 octahedra,  a cornercorner with one O(8)Li2Ti3 square pyramid, corners with two equivalent O(7)Li2Ti3 square pyramids, corners with three equivalent O(5)Li2Ti3 square pyramids,  a cornercorner with one O(1)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 2°. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(1), one Ti(3), and one Ti(4) atom to form distorted OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(6)Li3Ti3 octahedra, corners with two equivalent O(8)Li2Ti3 square pyramids, corners with three equivalent O(7)Li2Ti3 square pyramids,  a cornercorner with one O(1)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(3)Li2Ti3 trigonal bipyramid,  an edgeedge with one O(6)Li3Ti3 octahedra,  an edgeedge with one O(8)Li2Ti3 square pyramid, edges with two equivalent O(5)Li2Ti3 square pyramids,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-12°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Ti(1), one Ti(3), and one Ti(4) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(7)Li2Ti3 square pyramid,  a cornercorner with one O(8)Li2Ti3 square pyramid, corners with two equivalent O(1)Li2Ti3 trigonal bipyramids, corners with three equivalent O(3)Li2Ti3 trigonal bipyramids, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and edges with two equivalent O(4)Li2Ti3 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Ti(2), one Ti(3), and one Ti(4) atom to form a mixture of corner and edge-sharing OLi3Ti3 octahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Ti(1), one Ti(2), and one Ti(3) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(5)Li2Ti3 square pyramid,  a cornercorner with one O(8)Li2Ti3 square pyramid,  a cornercorner with one O(1)Li2Ti3 trigonal bipyramid, corners with two equivalent O(3)Li2Ti3 trigonal bipyramids, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(5)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Ti(1), one Ti(2), and one Ti(4) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(5)Li2Ti3 square pyramid,  a cornercorner with one O(7)Li2Ti3 square pyramid,  a cornercorner with one O(3)Li2Ti3 trigonal bipyramid, corners with two equivalent O(1)Li2Ti3 trigonal bipyramids, corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(5)Li2Ti3 square pyramid,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid,  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid.
Li3Ti4O8 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. The Li(1)-O(2) bond length is 2.09 Å. The Li(1)-O(3) bond length is 2.29 Å. The Li(1)-O(4) bond length is 2.01 Å. The Li(1)-O(6) bond length is 1.97 Å. The Li(1)-O(7) bond length is 1.96 Å. The Li(1)-O(8) bond length is 2.03 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO6 octahedra that share corners with three equivalent Ti(3)O6 octahedra, corners with four equivalent Li(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. The Li(2)-O(1) bond length is 1.99 Å. The Li(2)-O(2) bond length is 2.34 Å. The Li(2)-O(3) bond length is 2.11 Å. The Li(2)-O(5) bond length is 2.00 Å. The Li(2)-O(6) bond length is 1.97 Å. The Li(2)-O(7) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-54°. The Li(3)-O(1) bond length is 2.27 Å. The Li(3)-O(2) bond length is 2.04 Å. The Li(3)-O(4) bond length is 2.08 Å. The Li(3)-O(5) bond length is 2.00 Å. The Li(3)-O(6) bond length is 2.05 Å. The Li(3)-O(8) bond length is 2.02 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-50°. The Ti(1)-O(1) bond length is 2.01 Å. The Ti(1)-O(2) bond length is 2.17 Å. The Ti(1)-O(4) bond length is 2.02 Å. The Ti(1)-O(5) bond length is 2.06 Å. The Ti(1)-O(7) bond length is 2.02 Å. The Ti(1)-O(8) bond length is 1.95 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(4)O6 octahedra, corners with three equivalent Li(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. The Ti(2)-O(1) bond length is 2.00 Å. The Ti(2)-O(2) bond length is 2.11 Å. The Ti(2)-O(3) bond length is 2.14 Å. The Ti(2)-O(6) bond length is 2.06 Å. The Ti(2)-O(7) bond length is 2.01 Å. The Ti(2)-O(8) bond length is 1.98 Å. In the third Ti site, Ti(3) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with four equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-50°. The Ti(3)-O(2) bond length is 2.03 Å. The Ti(3)-O(3) bond length is 2.01 Å. The Ti(3)-O(4) bond length is 2.05 Å. The Ti(3)-O(5) bond length is 2.03 Å. The Ti(3)-O(6) bond length is 2.04 Å. The Ti(3)-O(7) bond length is 2.11 Å. In the fourth Ti site, Ti(4) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra, corners with four equivalent Ti(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-54°. The Ti(4)-O(1) bond length is 2.07 Å. The Ti(4)-O(3) bond length is 1.97 Å. The Ti(4)-O(4) bond length is 2.14 Å. The Ti(4)-O(5) bond length is 2.06 Å. The Ti(4)-O(6) bond length is 2.09 Å. The Ti(4)-O(8) bond length is 2.09 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Ti(1), one Ti(2), and one Ti(4) atom to form distorted OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(6)Li3Ti3 octahedra,  a cornercorner with one O(7)Li2Ti3 square pyramid, corners with two equivalent O(5)Li2Ti3 square pyramids, corners with two equivalent O(8)Li2Ti3 square pyramids,  a cornercorner with one O(3)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid,  an edgeedge with one O(6)Li3Ti3 octahedra,  an edgeedge with one O(5)Li2Ti3 square pyramid,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 6-7°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Ti(1), one Ti(2), and one Ti(3) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ti(2), one Ti(3), and one Ti(4) atom to form distorted OLi2Ti3 trigonal bipyramids that share  a cornercorner with one O(6)Li3Ti3 octahedra,  a cornercorner with one O(8)Li2Ti3 square pyramid, corners with two equivalent O(7)Li2Ti3 square pyramids, corners with three equivalent O(5)Li2Ti3 square pyramids,  a cornercorner with one O(1)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 2°. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(1), one Ti(3), and one Ti(4) atom to form distorted OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(6)Li3Ti3 octahedra, corners with two equivalent O(8)Li2Ti3 square pyramids, corners with three equivalent O(7)Li2Ti3 square pyramids,  a cornercorner with one O(1)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(3)Li2Ti3 trigonal bipyramid,  an edgeedge with one O(6)Li3Ti3 octahedra,  an edgeedge with one O(8)Li2Ti3 square pyramid, edges with two equivalent O(5)Li2Ti3 square pyramids,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 3-12°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Ti(1), one Ti(3), and one Ti(4) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(7)Li2Ti3 square pyramid,  a cornercorner with one O(8)Li2Ti3 square pyramid, corners with two equivalent O(1)Li2Ti3 trigonal bipyramids, corners with three equivalent O(3)Li2Ti3 trigonal bipyramids, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and edges with two equivalent O(4)Li2Ti3 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Ti(2), one Ti(3), and one Ti(4) atom to form a mixture of corner and edge-sharing OLi3Ti3 octahedra. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Ti(1), one Ti(2), and one Ti(3) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(5)Li2Ti3 square pyramid,  a cornercorner with one O(8)Li2Ti3 square pyramid,  a cornercorner with one O(1)Li2Ti3 trigonal bipyramid, corners with two equivalent O(3)Li2Ti3 trigonal bipyramids, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(5)Li2Ti3 square pyramid,  an edgeedge with one O(8)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Ti(1), one Ti(2), and one Ti(4) atom to form OLi2Ti3 square pyramids that share  a cornercorner with one O(5)Li2Ti3 square pyramid,  a cornercorner with one O(7)Li2Ti3 square pyramid,  a cornercorner with one O(3)Li2Ti3 trigonal bipyramid, corners with two equivalent O(1)Li2Ti3 trigonal bipyramids, corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(5)Li2Ti3 square pyramid,  an edgeedge with one O(7)Li2Ti3 square pyramid,  an edgeedge with one O(1)Li2Ti3 trigonal bipyramid,  an edgeedge with one O(3)Li2Ti3 trigonal bipyramid, and  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid.