Cs2RhF6 crystallizes in the trigonal P-3m1 space group. Cs(1) is bonded to twelve equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Rh(1)F6 octahedra, faces with eight equivalent Cs(1)F12 cuboctahedra, and faces with three equivalent Rh(1)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. Rh(1) is bonded to six equivalent F(1) atoms to form RhF6 octahedra that share corners with six equivalent Cs(1)F12 cuboctahedra and faces with six equivalent Cs(1)F12 cuboctahedra. F(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Rh(1) atom.
Cs2RhF6 crystallizes in the trigonal P-3m1 space group. Cs(1) is bonded to twelve equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with six equivalent Cs(1)F12 cuboctahedra, corners with three equivalent Rh(1)F6 octahedra, faces with eight equivalent Cs(1)F12 cuboctahedra, and faces with three equivalent Rh(1)F6 octahedra. The corner-sharing octahedral tilt angles are 17°. There are nine shorter (3.13 Å) and three longer (3.22 Å) Cs(1)-F(1) bond lengths. Rh(1) is bonded to six equivalent F(1) atoms to form RhF6 octahedra that share corners with six equivalent Cs(1)F12 cuboctahedra and faces with six equivalent Cs(1)F12 cuboctahedra. All Rh(1)-F(1) bond lengths are 1.93 Å. F(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Rh(1) atom.