Na3Ti2P2O10F crystallizes in the orthorhombic Fmm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent O(3), four equivalent O(2), and one F(1) atom. Ti(1) is bonded to one O(3), two equivalent O(1), two equivalent O(2), and one F(1) atom to form distorted TiO5F octahedra that share  a cornercorner with one Ti(1)O5F octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 46-50°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Ti(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ti(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(2), two equivalent Na(1), and one Ti(1) atom. F(1) is bonded in a square pyramidal geometry to one Na(2), two equivalent Na(1), and two equivalent Ti(1) atoms.
Na3Ti2P2O10F crystallizes in the orthorhombic Fmm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom. Both Na(1)-O(1) bond lengths are 2.60 Å. Both Na(1)-O(2) bond lengths are 2.47 Å. Both Na(1)-O(3) bond lengths are 2.56 Å. The Na(1)-F(1) bond length is 2.56 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent O(3), four equivalent O(2), and one F(1) atom. Both Na(2)-O(3) bond lengths are 2.51 Å. All Na(2)-O(2) bond lengths are 2.48 Å. The Na(2)-F(1) bond length is 2.33 Å. Ti(1) is bonded to one O(3), two equivalent O(1), two equivalent O(2), and one F(1) atom to form distorted TiO5F octahedra that share  a cornercorner with one Ti(1)O5F octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 9°. The Ti(1)-O(3) bond length is 1.70 Å. Both Ti(1)-O(1) bond lengths are 1.99 Å. Both Ti(1)-O(2) bond lengths are 2.09 Å. The Ti(1)-F(1) bond length is 2.16 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent Ti(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 46-50°. Both P(1)-O(1) bond lengths are 1.56 Å. Both P(1)-O(2) bond lengths are 1.55 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Ti(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ti(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(2), two equivalent Na(1), and one Ti(1) atom. F(1) is bonded in a square pyramidal geometry to one Na(2), two equivalent Na(1), and two equivalent Ti(1) atoms.