Li3Ti2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(8), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one Ti(3)O6 octahedra. In the second Li site, Li(2) is bonded to one O(8), one O(9), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-78°. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(2) atoms. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent P(2)O4 tetrahedra and edges with two equivalent Ti(2)O6 octahedra. In the second Ti site, Ti(2) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Ti(1)O6 octahedra. In the third Ti site, Ti(3) is bonded to two equivalent O(9) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent P(3)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(7), one O(8), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-57°. In the second P site, P(2) is bonded to one O(4), one O(6), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra and corners with three equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. In the third P site, P(3) is bonded to one O(5), one O(9), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-56°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ti(1), one Ti(2), and one P(2) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Ti(2), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2TiP trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ti(3), and one P(3) atom to form a mixture of distorted edge and corner-sharing OLi2TiP tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(3), one Ti(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Ti(3), and one P(3) atom.
Li3Ti2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(8), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one Ti(3)O6 octahedra. The Li(1)-O(5) bond length is 2.10 Å. The Li(1)-O(8) bond length is 2.12 Å. Both Li(1)-O(2) bond lengths are 2.28 Å. Both Li(1)-O(3) bond lengths are 2.27 Å. In the second Li site, Li(2) is bonded to one O(8), one O(9), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 67-78°. The Li(2)-O(8) bond length is 1.89 Å. The Li(2)-O(9) bond length is 1.99 Å. Both Li(2)-O(3) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(5), one O(6), and two equivalent O(2) atoms. The Li(3)-O(5) bond length is 1.93 Å. The Li(3)-O(6) bond length is 2.02 Å. Both Li(3)-O(2) bond lengths are 2.13 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent P(2)O4 tetrahedra and edges with two equivalent Ti(2)O6 octahedra. Both Ti(1)-O(4) bond lengths are 1.98 Å. All Ti(1)-O(1) bond lengths are 2.15 Å. In the second Ti site, Ti(2) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Ti(1)O6 octahedra. The Ti(2)-O(6) bond length is 2.06 Å. The Ti(2)-O(7) bond length is 1.95 Å. Both Ti(2)-O(1) bond lengths are 2.13 Å. Both Ti(2)-O(2) bond lengths are 2.10 Å. In the third Ti site, Ti(3) is bonded to two equivalent O(9) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, corners with six equivalent P(3)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Ti(3)-O(9) bond lengths are 2.03 Å. All Ti(3)-O(3) bond lengths are 2.08 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(7), one O(8), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-57°. The P(1)-O(7) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.51 Å. Both P(1)-O(2) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(4), one O(6), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra and corners with three equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-51°. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.55 Å. Both P(2)-O(1) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to one O(5), one O(9), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-56°. The P(3)-O(5) bond length is 1.51 Å. The P(3)-O(9) bond length is 1.56 Å. Both P(3)-O(3) bond lengths are 1.58 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ti(1), one Ti(2), and one P(2) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Ti(2), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2TiP trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ti(3), and one P(3) atom to form a mixture of distorted edge and corner-sharing OLi2TiP tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(3), one Ti(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Ti(3), and one P(3) atom.