Cs2NaAlF6 crystallizes in the trigonal R-3m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Al(1)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Al(2)F6 octahedra, and faces with four equivalent Na(1)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 11°. In the second Cs site, Cs(2) is bonded to three equivalent F(1) and nine equivalent F(2) atoms to form distorted CsF12 cuboctahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Na(1)F6 pentagonal pyramids, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra,  a faceface with one Al(2)F6 octahedra, faces with three equivalent Al(1)F6 octahedra, and faces with three equivalent Na(1)F6 pentagonal pyramids. Na(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted NaF6 pentagonal pyramids that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Al(2)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Al(1)F6 octahedra. The corner-sharing octahedral tilt angles are 8°. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to six equivalent F(2) atoms to form AlF6 octahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(2)F12 cuboctahedra, and faces with two equivalent Na(1)F6 pentagonal pyramids. In the second Al site, Al(2) is bonded to six equivalent F(1) atoms to form AlF6 octahedra that share corners with six equivalent Na(1)F6 pentagonal pyramids, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(1)F12 cuboctahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(1), one Na(1), and one Al(2) atom. In the second F site, F(2) is bonded in a 6-coordinate geometry to one Cs(1), three equivalent Cs(2), one Na(1), and one Al(1) atom.
Cs2NaAlF6 crystallizes in the trigonal R-3m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent F(2) and nine equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with six equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Al(1)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Al(2)F6 octahedra, and faces with four equivalent Na(1)F6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 11°. All Cs(1)-F(2) bond lengths are 3.19 Å. There are six shorter (3.20 Å) and three longer (3.39 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded to three equivalent F(1) and nine equivalent F(2) atoms to form distorted CsF12 cuboctahedra that share corners with three equivalent Cs(1)F12 cuboctahedra, corners with six equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Na(1)F6 pentagonal pyramids, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra,  a faceface with one Al(2)F6 octahedra, faces with three equivalent Al(1)F6 octahedra, and faces with three equivalent Na(1)F6 pentagonal pyramids. All Cs(2)-F(1) bond lengths are 3.22 Å. There are three shorter (3.12 Å) and six longer (3.16 Å) Cs(2)-F(2) bond lengths. Na(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted NaF6 pentagonal pyramids that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Al(2)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Al(1)F6 octahedra. The corner-sharing octahedral tilt angles are 8°. All Na(1)-F(1) bond lengths are 2.34 Å. All Na(1)-F(2) bond lengths are 2.39 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to six equivalent F(2) atoms to form AlF6 octahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(2)F12 cuboctahedra, and faces with two equivalent Na(1)F6 pentagonal pyramids. All Al(1)-F(2) bond lengths are 1.85 Å. In the second Al site, Al(2) is bonded to six equivalent F(1) atoms to form AlF6 octahedra that share corners with six equivalent Na(1)F6 pentagonal pyramids, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(1)F12 cuboctahedra. All Al(2)-F(1) bond lengths are 1.86 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(1), one Na(1), and one Al(2) atom. In the second F site, F(2) is bonded in a 6-coordinate geometry to one Cs(1), three equivalent Cs(2), one Na(1), and one Al(1) atom.