CsCoCl3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded to four equivalent Cl(2) and eight equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Co(1)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Co(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 15-16°. Co(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form CoCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Co(1)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Cs(1) and two equivalent Co(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°. In the second Cl site, Cl(2) is bonded to four equivalent Cs(1) and two equivalent Co(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°.
CsCoCl3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded to four equivalent Cl(2) and eight equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Co(1)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Co(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 15-16°. There are two shorter (3.63 Å) and two longer (3.74 Å) Cs(1)-Cl(2) bond lengths. There are a spread of Cs(1)-Cl(1) bond distances ranging from 3.62-3.75 Å. Co(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form CoCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Co(1)Cl6 octahedra. Both Co(1)-Cl(2) bond lengths are 2.46 Å. All Co(1)-Cl(1) bond lengths are 2.44 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Cs(1) and two equivalent Co(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°. In the second Cl site, Cl(2) is bonded to four equivalent Cs(1) and two equivalent Co(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°.