CsCdCl3 is (Cubic) Perovskite-like structured and crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent Cl(2) and nine equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra, corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cd(1)Cl6 octahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with four equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cd(2)Cl6 octahedra, and faces with four equivalent Cd(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the second Cs site, Cs(2) is bonded to six equivalent Cl(1) and six equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with two equivalent Cd(2)Cl6 octahedra, and faces with six equivalent Cd(1)Cl6 octahedra. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form CdCl6 octahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cd(2)Cl6 octahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with four equivalent Cs(1)Cl12 cuboctahedra, and  a faceface with one Cd(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 2°. In the second Cd site, Cd(2) is bonded to six equivalent Cl(1) atoms to form CdCl6 octahedra that share corners with six equivalent Cd(1)Cl6 octahedra, faces with two equivalent Cs(2)Cl12 cuboctahedra, and faces with six equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(1), one Cd(1), and one Cd(2) atom. In the second Cl site, Cl(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Cd(1) atoms to form a mixture of distorted corner and face-sharing ClCs4Cd2 octahedra. The corner-sharing octahedral tilt angles range from 3-60°.
CsCdCl3 is (Cubic) Perovskite-like structured and crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to three equivalent Cl(2) and nine equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra, corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cd(1)Cl6 octahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with four equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cd(2)Cl6 octahedra, and faces with four equivalent Cd(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. All Cs(1)-Cl(2) bond lengths are 3.75 Å. There are six shorter (3.73 Å) and three longer (3.83 Å) Cs(1)-Cl(1) bond lengths. In the second Cs site, Cs(2) is bonded to six equivalent Cl(1) and six equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with two equivalent Cd(2)Cl6 octahedra, and faces with six equivalent Cd(1)Cl6 octahedra. All Cs(2)-Cl(1) bond lengths are 3.79 Å. All Cs(2)-Cl(2) bond lengths are 3.73 Å. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form CdCl6 octahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cd(2)Cl6 octahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with four equivalent Cs(1)Cl12 cuboctahedra, and  a faceface with one Cd(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 2°. All Cd(1)-Cl(1) bond lengths are 2.61 Å. All Cd(1)-Cl(2) bond lengths are 2.66 Å. In the second Cd site, Cd(2) is bonded to six equivalent Cl(1) atoms to form CdCl6 octahedra that share corners with six equivalent Cd(1)Cl6 octahedra, faces with two equivalent Cs(2)Cl12 cuboctahedra, and faces with six equivalent Cs(1)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. All Cd(2)-Cl(1) bond lengths are 2.63 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted linear geometry to one Cs(2), three equivalent Cs(1), one Cd(1), and one Cd(2) atom. In the second Cl site, Cl(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Cd(1) atoms to form a mixture of distorted corner and face-sharing ClCs4Cd2 octahedra. The corner-sharing octahedral tilt angles range from 3-60°.