Li2Ti(PO3)5 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(10), one O(12), and one O(9) atom. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(12), one O(14), and one O(9) atom. Ti(1) is bonded to one O(1), one O(13), one O(15), one O(4), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are five inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(3), one O(6), and one O(9) atom to form corner-sharing PO4 tetrahedra. In the second P site, P(2) is bonded to one O(11), one O(15), one O(2), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-48°. In the third P site, P(3) is bonded to one O(13), one O(2), 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 33-39°. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-39°. In the fifth P site, P(5) is bonded to one O(12), one O(14), one O(3), and one O(5) atom to form corner-sharing PO4 tetrahedra. There are fifteen 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(4) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(5) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(4) and one P(5) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Li(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Li(2) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom.
Li2Ti(PO3)5 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(10), one O(12), and one O(9) atom. The Li(1)-O(10) bond length is 1.93 Å. The Li(1)-O(12) bond length is 1.95 Å. The Li(1)-O(9) bond length is 1.92 Å. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(12), one O(14), and one O(9) atom. The Li(2)-O(12) bond length is 1.88 Å. The Li(2)-O(14) bond length is 1.88 Å. The Li(2)-O(9) bond length is 1.92 Å. Ti(1) is bonded to one O(1), one O(13), one O(15), one O(4), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Ti(1)-O(1) bond length is 1.97 Å. The Ti(1)-O(13) bond length is 1.98 Å. The Ti(1)-O(15) bond length is 2.13 Å. The Ti(1)-O(4) bond length is 2.13 Å. The Ti(1)-O(7) bond length is 2.10 Å. The Ti(1)-O(8) bond length is 2.14 Å. There are five inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(3), one O(6), and one O(9) atom to form corner-sharing PO4 tetrahedra. The P(1)-O(10) bond length is 1.49 Å. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(6) bond length is 1.64 Å. The P(1)-O(9) bond length is 1.50 Å. In the second P site, P(2) is bonded to one O(11), one O(15), one O(2), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-48°. The P(2)-O(11) bond length is 1.63 Å. The P(2)-O(15) bond length is 1.50 Å. The P(2)-O(2) bond length is 1.63 Å. The P(2)-O(4) bond length is 1.51 Å. In the third P site, P(3) is bonded to one O(13), one O(2), 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 33-39°. The P(3)-O(13) bond length is 1.52 Å. The P(3)-O(2) bond length is 1.62 Å. The P(3)-O(6) bond length is 1.58 Å. The P(3)-O(7) bond length is 1.50 Å. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-39°. The P(4)-O(1) bond length is 1.52 Å. The P(4)-O(11) bond length is 1.62 Å. The P(4)-O(5) bond length is 1.58 Å. The P(4)-O(8) bond length is 1.51 Å. In the fifth P site, P(5) is bonded to one O(12), one O(14), one O(3), and one O(5) atom to form corner-sharing PO4 tetrahedra. The P(5)-O(12) bond length is 1.50 Å. The P(5)-O(14) bond length is 1.49 Å. The P(5)-O(3) bond length is 1.60 Å. The P(5)-O(5) bond length is 1.63 Å. There are fifteen 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(4) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(5) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(4) and one P(5) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Li(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Li(2) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 120 degrees geometry to one Ti(1) and one P(2) atom.