Li4Ti(TeO4)3 crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Te(3)O6 octahedra, and corners with four equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-81°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(5) atoms. Ti(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles are 43°. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TeO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra and edges with two equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles are 43°. In the second Te site, Te(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra, corners with four equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 56°. In the third Te site, Te(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(2)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles are 56°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Ti(1), and one Te(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Te(1), and one Te(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Ti(1), and one Te(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(3), one Te(1), and one Te(3) atom. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Ti(1), and one Te(2) atom to form distorted OLi2TiTe trigonal pyramids that share corners with two equivalent O(6)Li2Te2 tetrahedra, corners with two equivalent O(5)Li2TiTe trigonal pyramids, and  an edgeedge with one O(5)Li2TiTe trigonal pyramid. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Te(2), and one Te(3) atom to form distorted OLi2Te2 tetrahedra that share corners with four equivalent O(6)Li2Te2 tetrahedra and corners with two equivalent O(5)Li2TiTe trigonal pyramids.
Li4Ti(TeO4)3 crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(6) atoms. Both Li(1)-O(2) bond lengths are 1.98 Å. Both Li(1)-O(6) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Te(3)O6 octahedra, and corners with four equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-81°. Both Li(2)-O(3) bond lengths are 1.97 Å. Both Li(2)-O(6) bond lengths are 2.26 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms. Both Li(3)-O(1) bond lengths are 2.44 Å. Both Li(3)-O(4) bond lengths are 1.99 Å. Both Li(3)-O(5) bond lengths are 2.32 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(5) atoms. Both Li(4)-O(1) bond lengths are 2.28 Å. Both Li(4)-O(5) bond lengths are 2.01 Å. Ti(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles are 43°. Both Ti(1)-O(1) bond lengths are 1.96 Å. Both Ti(1)-O(3) bond lengths are 2.04 Å. Both Ti(1)-O(5) bond lengths are 1.98 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TeO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra and edges with two equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles are 43°. Both Te(1)-O(1) bond lengths are 1.95 Å. Both Te(1)-O(2) bond lengths are 1.97 Å. Both Te(1)-O(4) bond lengths are 1.96 Å. In the second Te site, Te(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra, corners with four equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 56°. Both Te(2)-O(3) bond lengths are 1.95 Å. Both Te(2)-O(5) bond lengths are 1.99 Å. Both Te(2)-O(6) bond lengths are 1.93 Å. In the third Te site, Te(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(2)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles are 56°. Both Te(3)-O(2) bond lengths are 2.11 Å. Both Te(3)-O(4) bond lengths are 2.12 Å. Both Te(3)-O(6) bond lengths are 2.33 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Ti(1), and one Te(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Te(1), and one Te(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Ti(1), and one Te(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(3), one Te(1), and one Te(3) atom. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Ti(1), and one Te(2) atom to form distorted OLi2TiTe trigonal pyramids that share corners with two equivalent O(6)Li2Te2 tetrahedra, corners with two equivalent O(5)Li2TiTe trigonal pyramids, and  an edgeedge with one O(5)Li2TiTe trigonal pyramid. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Te(2), and one Te(3) atom to form distorted OLi2Te2 tetrahedra that share corners with four equivalent O(6)Li2Te2 tetrahedra and corners with two equivalent O(5)Li2TiTe trigonal pyramids.