Na3AlF6 crystallizes in the orthorhombic Immm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent F(2) and four equivalent F(1) atoms. In the second Na site, Na(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. Al(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form AlF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. 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(2), two equivalent Na(1), and one Al(1) atom. In the second F site, F(2) is bonded in a distorted linear geometry to one Na(2), two equivalent Na(1), and one Al(1) atom.
Na3AlF6 crystallizes in the orthorhombic Immm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent F(2) and four equivalent F(1) atoms. Both Na(1)-F(2) bond lengths are 2.77 Å. All Na(1)-F(1) bond lengths are 2.62 Å. In the second Na site, Na(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both Na(2)-F(2) bond lengths are 2.21 Å. All Na(2)-F(1) bond lengths are 2.20 Å. Al(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form AlF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both Al(1)-F(2) bond lengths are 1.82 Å. All Al(1)-F(1) bond lengths are 1.82 Å. 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(2), two equivalent Na(1), and one Al(1) atom. In the second F site, F(2) is bonded in a distorted linear geometry to one Na(2), two equivalent Na(1), and one Al(1) atom.