Li2TiPO4F crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(5), one O(6), one O(7), and one F(2) atom to form distorted LiO4F trigonal bipyramids that share corners with two equivalent Ti(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent Ti(1)O4F2 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-56°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one O(8), and one F(1) atom. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(7), one F(1), and one F(2) atom to form distorted LiO4F2 octahedra that share corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O4F trigonal bipyramid, and faces with two equivalent Ti(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 32-40°. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(4), one O(5), one O(8), and one F(1) atom. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(4), one O(5), one O(6), one O(8), one F(1), and one F(2) atom to form TiO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Ti(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-68°. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), one O(3), one O(7), one F(1), and one F(2) atom to form TiO4F2 octahedra that share corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(1)O4F trigonal bipyramids, and faces with two equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 63-68°. There are two inequivalent P sites. In the first P site, P(1) 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 Li(3)O4F2 octahedra, corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent Ti(2)O4F2 octahedra,  a cornercorner with one Li(1)O4F trigonal bipyramid, and  an edgeedge with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-53°. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent Ti(2)O4F2 octahedra, and  a cornercorner with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 25-53°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Ti(2), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one Ti(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Ti(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Ti(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one Ti(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Ti(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Ti(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Ti(1), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Ti(1), and one Ti(2) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Ti(1), and one Ti(2) atom.
Li2TiPO4F crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(5), one O(6), one O(7), and one F(2) atom to form distorted LiO4F trigonal bipyramids that share corners with two equivalent Ti(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Li(3)O4F2 octahedra, edges with two equivalent Ti(1)O4F2 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-56°. The Li(1)-O(4) bond length is 2.02 Å. The Li(1)-O(5) bond length is 2.26 Å. The Li(1)-O(6) bond length is 1.96 Å. The Li(1)-O(7) bond length is 2.33 Å. The Li(1)-F(2) bond length is 1.89 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one O(8), and one F(1) atom. The Li(2)-O(1) bond length is 2.08 Å. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(5) bond length is 2.36 Å. The Li(2)-O(6) bond length is 1.97 Å. The Li(2)-O(8) bond length is 2.45 Å. The Li(2)-F(1) bond length is 2.23 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(7), one F(1), and one F(2) atom to form distorted LiO4F2 octahedra that share corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O4F trigonal bipyramid, and faces with two equivalent Ti(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 32-40°. The Li(3)-O(1) bond length is 2.20 Å. The Li(3)-O(2) bond length is 2.05 Å. The Li(3)-O(3) bond length is 2.39 Å. The Li(3)-O(7) bond length is 2.18 Å. The Li(3)-F(1) bond length is 2.00 Å. The Li(3)-F(2) bond length is 1.92 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(4), one O(5), one O(8), and one F(1) atom. The Li(4)-O(4) bond length is 1.91 Å. The Li(4)-O(5) bond length is 2.18 Å. The Li(4)-O(8) bond length is 1.96 Å. The Li(4)-F(1) bond length is 1.89 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(4), one O(5), one O(6), one O(8), one F(1), and one F(2) atom to form TiO4F2 octahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Ti(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-68°. The Ti(1)-O(4) bond length is 2.18 Å. The Ti(1)-O(5) bond length is 2.16 Å. The Ti(1)-O(6) bond length is 2.21 Å. The Ti(1)-O(8) bond length is 2.21 Å. The Ti(1)-F(1) bond length is 2.22 Å. The Ti(1)-F(2) bond length is 2.16 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), one O(3), one O(7), one F(1), and one F(2) atom to form TiO4F2 octahedra that share corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(1)O4F trigonal bipyramids, and faces with two equivalent Li(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 63-68°. The Ti(2)-O(1) bond length is 2.15 Å. The Ti(2)-O(2) bond length is 2.11 Å. The Ti(2)-O(3) bond length is 2.23 Å. The Ti(2)-O(7) bond length is 2.16 Å. The Ti(2)-F(1) bond length is 2.21 Å. The Ti(2)-F(2) bond length is 2.14 Å. There are two inequivalent P sites. In the first P site, P(1) 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 Li(3)O4F2 octahedra, corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent Ti(2)O4F2 octahedra,  a cornercorner with one Li(1)O4F trigonal bipyramid, and  an edgeedge with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-53°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.58 Å. The P(1)-O(6) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(3)O4F2 octahedra, corners with two equivalent Ti(1)O4F2 octahedra, corners with two equivalent Ti(2)O4F2 octahedra, and  a cornercorner with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 25-53°. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Ti(2), and one P(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one Ti(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Ti(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one Ti(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(4), one Ti(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Ti(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Ti(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Ti(1), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Ti(1), and one Ti(2) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Ti(1), and one Ti(2) atom.