Rb3CoCl5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to two equivalent Cl(2) and eight equivalent Cl(1) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent Cl(2) and six equivalent Cl(1) atoms. Co(1) is bonded in a tetrahedral geometry to four equivalent Cl(1) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to two equivalent Rb(1), three equivalent Rb(2), and one Co(1) atom. In the second Cl site, Cl(2) is bonded to two equivalent Rb(1) and four equivalent Rb(2) atoms to form corner-sharing ClRb6 octahedra. The corner-sharing octahedral tilt angles range from 0-38°.
Rb3CoCl5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to two equivalent Cl(2) and eight equivalent Cl(1) atoms. Both Rb(1)-Cl(2) bond lengths are 3.54 Å. All Rb(1)-Cl(1) bond lengths are 3.65 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to two equivalent Cl(2) and six equivalent Cl(1) atoms. Both Rb(2)-Cl(2) bond lengths are 3.30 Å. There are two shorter (3.25 Å) and four longer (3.46 Å) Rb(2)-Cl(1) bond lengths. Co(1) is bonded in a tetrahedral geometry to four equivalent Cl(1) atoms. All Co(1)-Cl(1) bond lengths are 2.25 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to two equivalent Rb(1), three equivalent Rb(2), and one Co(1) atom. In the second Cl site, Cl(2) is bonded to two equivalent Rb(1) and four equivalent Rb(2) atoms to form corner-sharing ClRb6 octahedra. The corner-sharing octahedral tilt angles range from 0-38°.