Li3Ti2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-68°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. In the second Ti site, Ti(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-49°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one Ti(2), and one P(1) atom to form distorted corner-sharing OLi2TiP tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Ti(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one P(1) atom.
Li3Ti2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-68°. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(4) bond length is 1.97 Å. There is one shorter (2.01 Å) and one longer (2.27 Å) Li(1)-O(2) bond length. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All Ti(1)-O(1) bond lengths are 1.98 Å. All Ti(1)-O(4) bond lengths are 2.12 Å. In the second Ti site, Ti(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. All Ti(2)-O(2) bond lengths are 2.09 Å. All Ti(2)-O(3) bond lengths are 2.06 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-49°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one Ti(2), and one P(1) atom to form distorted corner-sharing OLi2TiP tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Ti(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one P(1) atom.