Rb3PrF6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to twelve equivalent F(1) atoms to form distorted RbF12 cuboctahedra that share corners with twelve equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, faces with four equivalent Rb(2)F6 octahedra, and faces with four equivalent Pr(1)F6 octahedra. In the second Rb site, Rb(2) is bonded to six equivalent F(1) atoms to form RbF6 octahedra that share corners with six equivalent Pr(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Pr(1) is bonded to six equivalent F(1) atoms to form PrF6 octahedra that share corners with six equivalent Rb(2)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. F(1) is bonded in a linear geometry to one Rb(2), four equivalent Rb(1), and one Pr(1) atom.
Rb3PrF6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to twelve equivalent F(1) atoms to form distorted RbF12 cuboctahedra that share corners with twelve equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, faces with four equivalent Rb(2)F6 octahedra, and faces with four equivalent Pr(1)F6 octahedra. All Rb(1)-F(1) bond lengths are 3.52 Å. In the second Rb site, Rb(2) is bonded to six equivalent F(1) atoms to form RbF6 octahedra that share corners with six equivalent Pr(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Rb(2)-F(1) bond lengths are 2.67 Å. Pr(1) is bonded to six equivalent F(1) atoms to form PrF6 octahedra that share corners with six equivalent Rb(2)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Pr(1)-F(1) bond lengths are 2.30 Å. F(1) is bonded in a linear geometry to one Rb(2), four equivalent Rb(1), and one Pr(1) atom.