Li3Ti2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(4), and one O(6) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(5) and two equivalent O(6) atoms. Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-48°. In the second P site, P(2) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-47°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Ti(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Ti(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Ti(1), and one P(2) atom.
Li3Ti2(PO4)3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(4), and one O(6) atom. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(3) bond length is 2.17 Å. The Li(1)-O(4) bond length is 2.02 Å. The Li(1)-O(6) bond length is 2.18 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(5) and two equivalent O(6) atoms. Both Li(2)-O(5) bond lengths are 2.11 Å. Both Li(2)-O(6) bond lengths are 2.24 Å. Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. The Ti(1)-O(1) bond length is 2.09 Å. The Ti(1)-O(2) bond length is 1.94 Å. The Ti(1)-O(3) bond length is 2.08 Å. The Ti(1)-O(4) bond length is 2.06 Å. The Ti(1)-O(5) bond length is 2.11 Å. The Ti(1)-O(6) bond length is 2.07 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-48°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.55 Å. In the second P site, P(2) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-47°. Both P(2)-O(3) bond lengths are 1.54 Å. Both P(2)-O(6) bond lengths are 1.58 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Ti(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one Ti(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Ti(1), and one P(2) atom.