Cs2NaGaF6 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 Ga(2)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Ga(1)F6 octahedra, and faces with four equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 12°. 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 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra,  a faceface with one Ga(1)F6 octahedra, faces with three equivalent Na(1)F6 octahedra, and faces with three equivalent Ga(2)F6 octahedra. The corner-sharing octahedral tilt angles are 2°. Na(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted NaF6 octahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Ga(1)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Ga(2)F6 octahedra. The corner-sharing octahedral tilt angles are 8°. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to six equivalent F(1) atoms to form GaF6 octahedra that share corners with six equivalent Na(1)F6 octahedra, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 8°. In the second Ga site, Ga(2) is bonded to six equivalent F(2) atoms to form GaF6 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 octahedra. 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 Ga(1) 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 Ga(2) atom.
Cs2NaGaF6 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 Ga(2)F6 octahedra, faces with three equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F12 cuboctahedra, faces with three equivalent Ga(1)F6 octahedra, and faces with four equivalent Na(1)F6 octahedra. The corner-sharing octahedral tilt angles are 12°. All Cs(1)-F(2) bond lengths are 3.18 Å. There are six shorter (3.22 Å) and three longer (3.40 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 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra,  a faceface with one Ga(1)F6 octahedra, faces with three equivalent Na(1)F6 octahedra, and faces with three equivalent Ga(2)F6 octahedra. The corner-sharing octahedral tilt angles are 2°. All Cs(2)-F(1) bond lengths are 3.26 Å. There are three shorter (3.16 Å) and six longer (3.19 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 octahedra that share corners with three equivalent Cs(2)F12 cuboctahedra, corners with three equivalent Ga(1)F6 octahedra, faces with three equivalent Cs(2)F12 cuboctahedra, faces with four equivalent Cs(1)F12 cuboctahedra, and  a faceface with one Ga(2)F6 octahedra. The corner-sharing octahedral tilt angles are 8°. All Na(1)-F(1) bond lengths are 2.31 Å. All Na(1)-F(2) bond lengths are 2.40 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to six equivalent F(1) atoms to form GaF6 octahedra that share corners with six equivalent Na(1)F6 octahedra, faces with two equivalent Cs(2)F12 cuboctahedra, and faces with six equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedral tilt angles are 8°. All Ga(1)-F(1) bond lengths are 1.95 Å. In the second Ga site, Ga(2) is bonded to six equivalent F(2) atoms to form GaF6 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 octahedra. All Ga(2)-F(2) bond lengths are 1.94 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 Ga(1) 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 Ga(2) atom.