Na3V2O2(PO4)2F crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(18), one O(2), one O(6), one O(7), and one F(1) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(16), one O(17), one O(4), one O(8), and one F(2) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(14), one O(15), one O(18), one O(2), and one F(1) atom. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(14), one O(15), one O(19), one O(3), and one F(1) atom. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(13), one O(17), one O(20), one O(4), one O(5), one O(9), and one F(2) atom. In the sixth Na site, Na(6) is bonded in a 7-coordinate geometry to one O(12), one O(17), one O(20), one O(4), one O(5), one O(8), and one F(2) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(15), one O(2), one O(3), one O(4), one O(7), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one V(4)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. In the second V site, V(2) is bonded to one O(10), one O(16), one O(20), one O(8), one O(9), and one F(2) atom to form distorted VO5F octahedra that share  a cornercorner with one V(3)O5F octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 7°. In the third V site, V(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one F(2) atom to form distorted VO5F octahedra that share  a cornercorner with one V(2)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 7°. In the fourth V site, V(4) is bonded to one O(14), one O(17), one O(18), one O(19), one O(6), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one V(1)O5F octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. There are four 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 V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the second P site, P(2) is bonded to one O(14), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O5F octahedra and corners with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the third P site, P(3) is bonded to one O(12), one O(13), one O(15), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the fourth P site, P(4) is bonded to one O(16), one O(18), one O(19), and one O(20) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O5F octahedra and corners with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-50°. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one V(3), 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(3), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(4), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Na(5), one Na(6), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(5), one Na(6), one V(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(6), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(5), one V(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Na(4), and one V(2) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Na(4), and one V(3) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(6), one V(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(5), one V(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one V(4), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one V(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(2), one V(2), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one Na(2), one Na(5), one Na(6), and one V(4) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one V(4), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(4), one V(4), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted rectangular see-saw-like geometry to one Na(5), one Na(6), one V(2), and one P(4) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a square pyramidal geometry to one Na(1), one Na(3), one Na(4), one V(1), and one V(4) atom. In the second F site, F(2) is bonded in a square pyramidal geometry to one Na(2), one Na(5), one Na(6), one V(2), and one V(3) atom.
Na3V2O2(PO4)2F crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(18), one O(2), one O(6), one O(7), and one F(1) atom. The Na(1)-O(10) bond length is 2.50 Å. The Na(1)-O(11) bond length is 2.58 Å. The Na(1)-O(18) bond length is 2.40 Å. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(6) bond length is 2.66 Å. The Na(1)-O(7) bond length is 2.65 Å. The Na(1)-F(1) bond length is 2.61 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(16), one O(17), one O(4), one O(8), and one F(2) atom. The Na(2)-O(1) bond length is 2.67 Å. The Na(2)-O(12) bond length is 2.39 Å. The Na(2)-O(16) bond length is 2.66 Å. The Na(2)-O(17) bond length is 2.57 Å. The Na(2)-O(4) bond length is 2.50 Å. The Na(2)-O(8) bond length is 2.39 Å. The Na(2)-F(2) bond length is 2.60 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(14), one O(15), one O(18), one O(2), and one F(1) atom. The Na(3)-O(10) bond length is 2.58 Å. The Na(3)-O(11) bond length is 2.59 Å. The Na(3)-O(14) bond length is 2.43 Å. The Na(3)-O(15) bond length is 2.41 Å. The Na(3)-O(18) bond length is 2.45 Å. The Na(3)-O(2) bond length is 2.47 Å. The Na(3)-F(1) bond length is 2.34 Å. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(14), one O(15), one O(19), one O(3), and one F(1) atom. The Na(4)-O(10) bond length is 2.68 Å. The Na(4)-O(11) bond length is 2.59 Å. The Na(4)-O(14) bond length is 2.42 Å. The Na(4)-O(15) bond length is 2.42 Å. The Na(4)-O(19) bond length is 2.48 Å. The Na(4)-O(3) bond length is 2.47 Å. The Na(4)-F(1) bond length is 2.45 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(13), one O(17), one O(20), one O(4), one O(5), one O(9), and one F(2) atom. The Na(5)-O(13) bond length is 2.66 Å. The Na(5)-O(17) bond length is 2.50 Å. The Na(5)-O(20) bond length is 2.38 Å. The Na(5)-O(4) bond length is 2.57 Å. The Na(5)-O(5) bond length is 2.38 Å. The Na(5)-O(9) bond length is 2.67 Å. The Na(5)-F(2) bond length is 2.60 Å. In the sixth Na site, Na(6) is bonded in a 7-coordinate geometry to one O(12), one O(17), one O(20), one O(4), one O(5), one O(8), and one F(2) atom. The Na(6)-O(12) bond length is 2.43 Å. The Na(6)-O(17) bond length is 2.59 Å. The Na(6)-O(20) bond length is 2.43 Å. The Na(6)-O(4) bond length is 2.59 Å. The Na(6)-O(5) bond length is 2.46 Å. The Na(6)-O(8) bond length is 2.45 Å. The Na(6)-F(2) bond length is 2.34 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(15), one O(2), one O(3), one O(4), one O(7), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one V(4)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. The V(1)-O(15) bond length is 2.08 Å. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 1.68 Å. The V(1)-O(7) bond length is 2.01 Å. The V(1)-F(1) bond length is 2.12 Å. In the second V site, V(2) is bonded to one O(10), one O(16), one O(20), one O(8), one O(9), and one F(2) atom to form distorted VO5F octahedra that share  a cornercorner with one V(3)O5F octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 7°. The V(2)-O(10) bond length is 1.68 Å. The V(2)-O(16) bond length is 2.02 Å. The V(2)-O(20) bond length is 2.08 Å. The V(2)-O(8) bond length is 2.07 Å. The V(2)-O(9) bond length is 2.01 Å. The V(2)-F(2) bond length is 2.11 Å. In the third V site, V(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one F(2) atom to form distorted VO5F octahedra that share  a cornercorner with one V(2)O5F octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 7°. The V(3)-O(1) bond length is 2.01 Å. The V(3)-O(11) bond length is 1.68 Å. The V(3)-O(12) bond length is 2.07 Å. The V(3)-O(13) bond length is 2.01 Å. The V(3)-O(5) bond length is 2.08 Å. The V(3)-F(2) bond length is 2.11 Å. In the fourth V site, V(4) is bonded to one O(14), one O(17), one O(18), one O(19), one O(6), and one F(1) atom to form distorted VO5F octahedra that share  a cornercorner with one V(1)O5F octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 6°. The V(4)-O(14) bond length is 2.08 Å. The V(4)-O(17) bond length is 1.68 Å. The V(4)-O(18) bond length is 2.07 Å. The V(4)-O(19) bond length is 2.02 Å. The V(4)-O(6) bond length is 2.01 Å. The V(4)-F(1) bond length is 2.12 Å. There are four 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 V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.56 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(14), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O5F octahedra and corners with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The P(2)-O(14) 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 1.56 Å. The P(2)-O(9) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(12), one O(13), one O(15), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The P(3)-O(12) bond length is 1.56 Å. The P(3)-O(13) bond length is 1.55 Å. The P(3)-O(15) bond length is 1.56 Å. The P(3)-O(7) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(16), one O(18), one O(19), and one O(20) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O5F octahedra and corners with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The P(4)-O(16) bond length is 1.55 Å. The P(4)-O(18) bond length is 1.56 Å. The P(4)-O(19) bond length is 1.55 Å. The P(4)-O(20) bond length is 1.55 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one V(3), 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(3), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(4), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Na(5), one Na(6), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(5), one Na(6), one V(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one V(4), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(6), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(5), one V(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Na(4), and one V(2) atom. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Na(4), and one V(3) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(6), one V(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(5), one V(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one V(4), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(4), one V(1), and one P(3) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(2), one V(2), and one P(4) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one Na(2), one Na(5), one Na(6), and one V(4) atom. In the eighteenth O site, O(18) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one V(4), and one P(4) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(4), one V(4), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted rectangular see-saw-like geometry to one Na(5), one Na(6), one V(2), and one P(4) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a square pyramidal geometry to one Na(1), one Na(3), one Na(4), one V(1), and one V(4) atom. In the second F site, F(2) is bonded in a square pyramidal geometry to one Na(2), one Na(5), one Na(6), one V(2), and one V(3) atom.