CsCrCl3 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded to four equivalent Cl(1) and eight equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cr(1)Cl6 octahedra, corners with three equivalent Cr(2)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cr(1)Cl6 octahedra, and faces with three equivalent Cr(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 11-25°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CrCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Cr(2)Cl6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CrCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Cr(1)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Cr(1), and one Cr(2) atom. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to four equivalent Cs(1), one Cr(1), and one Cr(2) atom.
CsCrCl3 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded to four equivalent Cl(1) and eight equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cr(1)Cl6 octahedra, corners with three equivalent Cr(2)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cr(1)Cl6 octahedra, and faces with three equivalent Cr(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 11-25°. There are a spread of Cs(1)-Cl(1) bond distances ranging from 3.64-3.97 Å. There are a spread of Cs(1)-Cl(2) bond distances ranging from 3.65-3.92 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CrCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Cr(2)Cl6 octahedra. Both Cr(1)-Cl(1) bond lengths are 2.77 Å. All Cr(1)-Cl(2) bond lengths are 2.41 Å. In the second Cr site, Cr(2) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form CrCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Cr(1)Cl6 octahedra. Both Cr(2)-Cl(1) bond lengths are 2.38 Å. All Cr(2)-Cl(2) bond lengths are 2.59 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Cr(1), and one Cr(2) atom. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to four equivalent Cs(1), one Cr(1), and one Cr(2) atom.