Na3Al2P2O8F3 crystallizes in the orthorhombic Cmc2_1 space group. There are three 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(4), one F(1), and two equivalent F(2) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(4), one F(1), and two equivalent F(2) atoms. In the third Na site, Na(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(2) atoms to form distorted NaO4F2 pentagonal pyramids that share corners with six equivalent Al(1)O4F2 octahedra and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-57°. Al(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form AlO4F2 octahedra that share  a cornercorner with one Al(1)O4F2 octahedra, corners with three equivalent Na(3)O4F2 pentagonal pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 5°. 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 corners with four equivalent Al(1)O4F2 octahedra and  an edgeedge with one Na(3)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 42-45°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Al(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(3), one Al(1), 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(2), one Al(1), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), and two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one Al(1) atom.
Na3Al2P2O8F3 crystallizes in the orthorhombic Cmc2_1 space group. There are three 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(4), one F(1), and two equivalent F(2) atoms. Both Na(1)-O(1) bond lengths are 2.46 Å. Both Na(1)-O(4) bond lengths are 2.39 Å. The Na(1)-F(1) bond length is 2.45 Å. Both Na(1)-F(2) bond lengths are 2.47 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(4), one F(1), and two equivalent F(2) atoms. Both Na(2)-O(2) bond lengths are 2.40 Å. Both Na(2)-O(4) bond lengths are 2.48 Å. The Na(2)-F(1) bond length is 2.43 Å. Both Na(2)-F(2) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(2) atoms to form distorted NaO4F2 pentagonal pyramids that share corners with six equivalent Al(1)O4F2 octahedra and edges with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-57°. Both Na(3)-O(2) bond lengths are 2.55 Å. Both Na(3)-O(3) bond lengths are 2.46 Å. Both Na(3)-F(2) bond lengths are 2.39 Å. Al(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form AlO4F2 octahedra that share  a cornercorner with one Al(1)O4F2 octahedra, corners with three equivalent Na(3)O4F2 pentagonal pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 5°. The Al(1)-O(1) bond length is 1.90 Å. The Al(1)-O(2) bond length is 1.90 Å. The Al(1)-O(3) bond length is 1.88 Å. The Al(1)-O(4) bond length is 1.95 Å. The Al(1)-F(1) bond length is 1.90 Å. The Al(1)-F(2) bond length is 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 corners with four equivalent Al(1)O4F2 octahedra and  an edgeedge with one Na(3)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 42-45°. 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 1.54 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Al(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Al(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(3), one Al(1), 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(2), one Al(1), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), and two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one Al(1) atom.