Cs3GdCl6 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 Cl(1) atoms to form distorted CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Cs(2)Cl6 octahedra, and faces with four equivalent Gd(1)Cl6 octahedra. In the second Cs site, Cs(2) is bonded to six equivalent Cl(1) atoms to form CsCl6 octahedra that share corners with six equivalent Gd(1)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. Gd(1) is bonded to six equivalent Cl(1) atoms to form GdCl6 octahedra that share corners with six equivalent Cs(2)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. Cl(1) is bonded in a linear geometry to one Cs(2), four equivalent Cs(1), and one Gd(1) atom.
Cs3GdCl6 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 Cl(1) atoms to form distorted CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Cs(2)Cl6 octahedra, and faces with four equivalent Gd(1)Cl6 octahedra. All Cs(1)-Cl(1) bond lengths are 4.23 Å. In the second Cs site, Cs(2) is bonded to six equivalent Cl(1) atoms to form CsCl6 octahedra that share corners with six equivalent Gd(1)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. All Cs(2)-Cl(1) bond lengths are 3.29 Å. Gd(1) is bonded to six equivalent Cl(1) atoms to form GdCl6 octahedra that share corners with six equivalent Cs(2)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. All Gd(1)-Cl(1) bond lengths are 2.67 Å. Cl(1) is bonded in a linear geometry to one Cs(2), four equivalent Cs(1), and one Gd(1) atom.