Na5Al3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent F(1) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent F(2), two equivalent F(3), and four equivalent F(1) atoms. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 33°. In the second Al site, Al(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 33°. There are three inequivalent F sites. In the first F site, F(2) is bonded in a distorted single-bond geometry to four equivalent Na(2) and one Al(1) atom. In the second F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Na(2), one Al(1), and one Al(2) atom. In the third F site, F(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Al(2) atom.
Na5Al3F14 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a body-centered cubic geometry to eight equivalent F(1) atoms. All Na(1)-F(1) bond lengths are 2.56 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent F(2), two equivalent F(3), and four equivalent F(1) atoms. Both Na(2)-F(2) bond lengths are 2.59 Å. Both Na(2)-F(3) bond lengths are 2.78 Å. There are two shorter (2.24 Å) and two longer (2.26 Å) Na(2)-F(1) bond lengths. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent F(2) and four equivalent F(3) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 33°. Both Al(1)-F(2) bond lengths are 1.80 Å. All Al(1)-F(3) bond lengths are 1.79 Å. In the second Al site, Al(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form corner-sharing AlF6 octahedra. The corner-sharing octahedral tilt angles are 33°. Both Al(2)-F(3) bond lengths are 1.82 Å. All Al(2)-F(1) bond lengths are 1.79 Å. There are three inequivalent F sites. In the first F site, F(2) is bonded in a distorted single-bond geometry to four equivalent Na(2) and one Al(1) atom. In the second F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Na(2), one Al(1), and one Al(2) atom. In the third F site, F(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Al(2) atom.