Na3MgTi2P2O10F crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(9), and one F(1) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(7), one O(9), and one F(1) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(7), one O(8), and one F(1) atom. Mg(1) is bonded in a 7-coordinate geometry to one O(10), one O(2), one O(4), one O(5), one O(7), 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(10), one O(2), one O(3), one O(4), one O(6), and one F(1) atom to form distorted TiO5F octahedra that share  a cornercorner with one Ti(2)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 12°. In the second Ti site, Ti(2) is bonded to one O(1), one O(5), one O(7), one O(8), one O(9), and one F(1) atom to form distorted TiO5F octahedra that share  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 12°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O5F octahedra and corners with two equivalent Ti(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second P site, P(2) is bonded to one O(10), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O5F octahedra and corners with two equivalent Ti(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-54°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ti(2), 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(3), one Mg(1), one Ti(1), and one P(1) atom. In the third O site, O(3) 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 fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mg(1), and one Ti(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Mg(1), one Ti(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ti(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mg(1), and one Ti(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Mg(1), one Ti(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ti(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Mg(1), one Ti(1), and one P(2) atom. F(1) is bonded in an octahedral geometry to one Na(1), one Na(2), one Na(3), one Mg(1), one Ti(1), and one Ti(2) atom.
Na3MgTi2P2O10F crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(9), and one F(1) atom. The Na(1)-O(1) bond length is 2.41 Å. The Na(1)-O(3) bond length is 2.40 Å. The Na(1)-O(6) bond length is 2.41 Å. The Na(1)-O(9) bond length is 2.41 Å. The Na(1)-F(1) bond length is 2.59 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(7), one O(9), and one F(1) atom. The Na(2)-O(10) bond length is 2.44 Å. The Na(2)-O(3) bond length is 2.40 Å. The Na(2)-O(4) bond length is 2.62 Å. The Na(2)-O(5) bond length is 2.43 Å. The Na(2)-O(7) bond length is 2.61 Å. The Na(2)-O(9) bond length is 2.40 Å. The Na(2)-F(1) bond length is 2.48 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(7), one O(8), and one F(1) atom. The Na(3)-O(1) bond length is 2.38 Å. The Na(3)-O(2) bond length is 2.50 Å. The Na(3)-O(4) bond length is 2.57 Å. The Na(3)-O(6) bond length is 2.38 Å. The Na(3)-O(7) bond length is 2.58 Å. The Na(3)-O(8) bond length is 2.50 Å. The Na(3)-F(1) bond length is 2.57 Å. Mg(1) is bonded in a 7-coordinate geometry to one O(10), one O(2), one O(4), one O(5), one O(7), one O(8), and one F(1) atom. The Mg(1)-O(10) bond length is 2.54 Å. The Mg(1)-O(2) bond length is 2.28 Å. The Mg(1)-O(4) bond length is 2.13 Å. The Mg(1)-O(5) bond length is 2.56 Å. The Mg(1)-O(7) bond length is 2.14 Å. The Mg(1)-O(8) bond length is 2.29 Å. The Mg(1)-F(1) bond length is 2.28 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(10), one O(2), one O(3), one O(4), one O(6), and one F(1) atom to form distorted TiO5F octahedra that share  a cornercorner with one Ti(2)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 12°. The Ti(1)-O(10) bond length is 2.15 Å. The Ti(1)-O(2) bond length is 2.20 Å. The Ti(1)-O(3) bond length is 2.12 Å. The Ti(1)-O(4) bond length is 1.77 Å. The Ti(1)-O(6) bond length is 2.13 Å. The Ti(1)-F(1) bond length is 2.18 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(5), one O(7), one O(8), one O(9), and one F(1) atom to form distorted TiO5F octahedra that share  a cornercorner with one Ti(1)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 12°. The Ti(2)-O(1) bond length is 2.13 Å. The Ti(2)-O(5) bond length is 2.15 Å. The Ti(2)-O(7) bond length is 1.77 Å. The Ti(2)-O(8) bond length is 2.20 Å. The Ti(2)-O(9) bond length is 2.12 Å. The Ti(2)-F(1) bond length is 2.18 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(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O5F octahedra and corners with two equivalent Ti(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(10), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O5F octahedra and corners with two equivalent Ti(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.57 Å. The P(2)-O(9) bond length is 1.55 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ti(2), 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(3), one Mg(1), one Ti(1), and one P(1) atom. In the third O site, O(3) 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 fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mg(1), and one Ti(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Mg(1), one Ti(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ti(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Mg(1), and one Ti(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Mg(1), one Ti(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ti(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Mg(1), one Ti(1), and one P(2) atom. F(1) is bonded in an octahedral geometry to one Na(1), one Na(2), one Na(3), one Mg(1), one Ti(1), and one Ti(2) atom.