CsTlCl3 is (Cubic) Perovskite-like structured and crystallizes in the cubic Fm-3m space group. Cs(1) is bonded to twelve equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Tl(1)Cl6 octahedra, and faces with four equivalent Tl(2)Cl6 octahedra. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to six equivalent Cl(1) atoms to form TlCl6 octahedra that share corners with six equivalent Tl(2)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. In the second Tl site, Tl(2) is bonded to six equivalent Cl(1) atoms to form TlCl6 octahedra that share corners with six equivalent Tl(1)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. Cl(1) is bonded to four equivalent Cs(1), one Tl(1), and one Tl(2) atom to form a mixture of distorted corner, edge, and face-sharing ClCs4Tl2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°.
CsTlCl3 is (Cubic) Perovskite-like structured and crystallizes in the cubic Fm-3m space group. Cs(1) is bonded to twelve equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with four equivalent Tl(1)Cl6 octahedra, and faces with four equivalent Tl(2)Cl6 octahedra. All Cs(1)-Cl(1) bond lengths are 3.95 Å. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to six equivalent Cl(1) atoms to form TlCl6 octahedra that share corners with six equivalent Tl(2)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. All Tl(1)-Cl(1) bond lengths are 2.98 Å. In the second Tl site, Tl(2) is bonded to six equivalent Cl(1) atoms to form TlCl6 octahedra that share corners with six equivalent Tl(1)Cl6 octahedra and faces with eight equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. All Tl(2)-Cl(1) bond lengths are 2.61 Å. Cl(1) is bonded to four equivalent Cs(1), one Tl(1), and one Tl(2) atom to form a mixture of distorted corner, edge, and face-sharing ClCs4Tl2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°.