LiTi(PO3)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 4-coordinate geometry to four equivalent O(4) atoms. Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. In the second P site, P(2) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-47°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms. In the third O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom. In the fourth O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(1) atom.
LiTi(PO3)4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 4-coordinate geometry to four equivalent O(4) atoms. There are two shorter (2.16 Å) and two longer (2.47 Å) Li(1)-O(4) bond lengths. Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Ti(1)-O(2) bond lengths are 2.02 Å. Both Ti(1)-O(3) bond lengths are 2.08 Å. Both Ti(1)-O(7) bond lengths are 2.05 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The P(1)-O(1) bond length is 1.62 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.49 Å. The P(1)-O(5) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(2), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-47°. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.51 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the second O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent P(2) atoms. In the third O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom. In the fourth O site, O(1) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(1) atom.