Rb2CrCl4 is (La,Ba)CuO4 structured and crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 9-coordinate geometry to four equivalent Cl(1) and five equivalent Cl(2) atoms. Cr(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form corner-sharing CrCl6 octahedra. The corner-sharing octahedra are not tilted. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Rb(1) and two equivalent Cr(1) atoms to form ClRb4Cr2 octahedra that share corners with two equivalent Cl(1)Rb4Cr2 octahedra, corners with twelve equivalent Cl(2)Rb5Cr octahedra, edges with two equivalent Cl(1)Rb4Cr2 octahedra, faces with four equivalent Cl(1)Rb4Cr2 octahedra, and faces with four equivalent Cl(2)Rb5Cr octahedra. The corner-sharing octahedral tilt angles range from 0-56°. In the second Cl site, Cl(2) is bonded to five equivalent Rb(1) and one Cr(1) atom to form distorted ClRb5Cr octahedra that share corners with five equivalent Cl(2)Rb5Cr octahedra, corners with twelve equivalent Cl(1)Rb4Cr2 octahedra, edges with eight equivalent Cl(2)Rb5Cr octahedra, and faces with four equivalent Cl(1)Rb4Cr2 octahedra. The corner-sharing octahedral tilt angles range from 0-56°.
Rb2CrCl4 is (La,Ba)CuO4 structured and crystallizes in the monoclinic C2/m space group. Rb(1) is bonded in a 9-coordinate geometry to four equivalent Cl(1) and five equivalent Cl(2) atoms. All Rb(1)-Cl(1) bond lengths are 3.36 Å. There are a spread of Rb(1)-Cl(2) bond distances ranging from 3.30-3.57 Å. Cr(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form corner-sharing CrCl6 octahedra. The corner-sharing octahedra are not tilted. Both Cr(1)-Cl(2) bond lengths are 2.44 Å. All Cr(1)-Cl(1) bond lengths are 2.52 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Rb(1) and two equivalent Cr(1) atoms to form ClRb4Cr2 octahedra that share corners with two equivalent Cl(1)Rb4Cr2 octahedra, corners with twelve equivalent Cl(2)Rb5Cr octahedra, edges with two equivalent Cl(1)Rb4Cr2 octahedra, faces with four equivalent Cl(1)Rb4Cr2 octahedra, and faces with four equivalent Cl(2)Rb5Cr octahedra. The corner-sharing octahedral tilt angles range from 0-56°. In the second Cl site, Cl(2) is bonded to five equivalent Rb(1) and one Cr(1) atom to form distorted ClRb5Cr octahedra that share corners with five equivalent Cl(2)Rb5Cr octahedra, corners with twelve equivalent Cl(1)Rb4Cr2 octahedra, edges with eight equivalent Cl(2)Rb5Cr octahedra, and faces with four equivalent Cl(1)Rb4Cr2 octahedra. The corner-sharing octahedral tilt angles range from 0-56°.