Cs3AsF6 is (Cubic) Perovskite-like structured and 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 As(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 As(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. As(1) is bonded to six equivalent F(1) atoms to form AsF6 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 distorted linear geometry to one Cs(2), four equivalent Cs(1), and one As(1) atom.
Cs3AsF6 is (Cubic) Perovskite-like structured and 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 As(1)F6 octahedra. All Cs(1)-F(1) bond lengths are 3.44 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 As(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 2.78 Å. As(1) is bonded to six equivalent F(1) atoms to form AsF6 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 As(1)-F(1) bond lengths are 2.05 Å. F(1) is bonded in a distorted linear geometry to one Cs(2), four equivalent Cs(1), and one As(1) atom.