Na5Al(PO4)2F2 crystallizes in the trigonal P-3 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(4) and three equivalent F(1) atoms to form NaO3F3 octahedra that share corners with three equivalent Al(1)O4F2 octahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Na(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 28°. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent F(1) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), two equivalent O(3), and one F(1) atom. In the fourth Na site, Na(4) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O3F3 octahedra, and edges with two equivalent Al(1)O4F2 octahedra. In the fifth Na site, Na(5) is bonded to six equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Na(6)O6 octahedra. In the sixth Na site, Na(6) is bonded to six equivalent O(3) atoms to form NaO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Na(5)O6 octahedra. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent Na(1)O3F3 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Na(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 28°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O3F3 octahedra,  a cornercorner with one Na(5)O6 octahedra,  a cornercorner with one Na(6)O6 octahedra, corners with two equivalent Na(4)O4F2 octahedra, and corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 31-68°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), one Al(1), and one P(1) atom to form distorted corner-sharing ONa2AlP trigonal pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Al(1), and one P(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(5), one Na(6), two equivalent Na(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(4), and one P(1) atom. F(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), and one Al(1) atom.
Na5Al(PO4)2F2 crystallizes in the trigonal P-3 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(4) and three equivalent F(1) atoms to form NaO3F3 octahedra that share corners with three equivalent Al(1)O4F2 octahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with three equivalent Na(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 28°. All Na(1)-O(4) bond lengths are 2.36 Å. All Na(1)-F(1) bond lengths are 2.40 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent F(1) atoms. All Na(2)-O(1) bond lengths are 2.38 Å. All Na(2)-O(2) bond lengths are 2.84 Å. All Na(2)-F(1) bond lengths are 2.36 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), two equivalent O(3), and one F(1) atom. The Na(3)-O(1) bond length is 2.48 Å. The Na(3)-O(2) bond length is 2.61 Å. The Na(3)-O(4) bond length is 2.35 Å. There is one shorter (2.49 Å) and one longer (2.59 Å) Na(3)-O(3) bond length. The Na(3)-F(1) bond length is 2.39 Å. In the fourth Na site, Na(4) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Na(1)O3F3 octahedra, and edges with two equivalent Al(1)O4F2 octahedra. Both Na(4)-O(2) bond lengths are 2.43 Å. Both Na(4)-O(4) bond lengths are 2.33 Å. Both Na(4)-F(1) bond lengths are 2.47 Å. In the fifth Na site, Na(5) is bonded to six equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Na(6)O6 octahedra. All Na(5)-O(3) bond lengths are 2.52 Å. In the sixth Na site, Na(6) is bonded to six equivalent O(3) atoms to form NaO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Na(5)O6 octahedra. All Na(6)-O(3) bond lengths are 2.47 Å. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent Na(1)O3F3 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Na(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 28°. Both Al(1)-O(1) bond lengths are 1.90 Å. Both Al(1)-O(2) bond lengths are 1.92 Å. Both Al(1)-F(1) bond lengths are 1.85 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O3F3 octahedra,  a cornercorner with one Na(5)O6 octahedra,  a cornercorner with one Na(6)O6 octahedra, corners with two equivalent Na(4)O4F2 octahedra, and corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 31-68°. The P(1)-O(1) bond length is 1.57 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(4) bond length is 1.54 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), one Al(1), and one P(1) atom to form distorted corner-sharing ONa2AlP trigonal pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Al(1), and one P(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(5), one Na(6), two equivalent Na(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(4), and one P(1) atom. F(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), and one Al(1) atom.