Cs3ScF6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to twelve equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with twelve equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F6 octahedra, and faces with four equivalent Sc(1)F6 octahedra. In the second Cs site, Cs(2) is bonded to six equivalent F(1) atoms to form CsF6 octahedra that share corners with six equivalent Sc(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Sc(1) is bonded to six equivalent F(1) atoms to form ScF6 octahedra that share corners with six equivalent Cs(2)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. F(1) is bonded in a 2-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Sc(1) atom.
Cs3ScF6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to twelve equivalent F(1) atoms to form CsF12 cuboctahedra that share corners with twelve equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F6 octahedra, and faces with four equivalent Sc(1)F6 octahedra. All Cs(1)-F(1) bond lengths are 3.42 Å. In the second Cs site, Cs(2) is bonded to six equivalent F(1) atoms to form CsF6 octahedra that share corners with six equivalent Sc(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Cs(2)-F(1) bond lengths are 2.79 Å. Sc(1) is bonded to six equivalent F(1) atoms to form ScF6 octahedra that share corners with six equivalent Cs(2)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Sc(1)-F(1) bond lengths are 2.02 Å. F(1) is bonded in a 2-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Sc(1) atom.