Cs2NaAl3F12 crystallizes in the trigonal R-3m space group. Cs(1) is bonded in a 15-coordinate geometry to six equivalent F(2) and nine equivalent F(1) atoms. Na(1) is bonded to six equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. Al(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form AlF6 octahedra that share corners with two equivalent Na(1)F6 octahedra and corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-51°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to three equivalent Cs(1), one Na(1), and one Al(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Cs(1) and two equivalent Al(1) atoms.
Cs2NaAl3F12 crystallizes in the trigonal R-3m space group. Cs(1) is bonded in a 15-coordinate geometry to six equivalent F(2) and nine equivalent F(1) atoms. There are three shorter (3.38 Å) and three longer (3.51 Å) Cs(1)-F(2) bond lengths. There are three shorter (3.06 Å) and six longer (3.61 Å) Cs(1)-F(1) bond lengths. Na(1) is bonded to six equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. All Na(1)-F(1) bond lengths are 2.33 Å. Al(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form AlF6 octahedra that share corners with two equivalent Na(1)F6 octahedra and corners with four equivalent Al(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-51°. Both Al(1)-F(1) bond lengths are 1.78 Å. All Al(1)-F(2) bond lengths are 1.86 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to three equivalent Cs(1), one Na(1), and one Al(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent Cs(1) and two equivalent Al(1) atoms.