RbCuCl3 crystallizes in the tetragonal I4/mcm space group. Rb(1) is bonded to four equivalent Cl(2) and eight equivalent Cl(1) atoms to form RbCl12 cuboctahedra that share corners with twelve equivalent Rb(1)Cl12 cuboctahedra, faces with six equivalent Rb(1)Cl12 cuboctahedra, and faces with eight equivalent Cu(1)Cl6 octahedra. Cu(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form CuCl6 octahedra that share corners with six equivalent Cu(1)Cl6 octahedra and faces with eight equivalent Rb(1)Cl12 cuboctahedra. 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 Cu(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClRb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. In the second Cl site, Cl(2) is bonded in a distorted linear geometry to four equivalent Rb(1) and two equivalent Cu(1) atoms.
RbCuCl3 crystallizes in the tetragonal I4/mcm space group. Rb(1) is bonded to four equivalent Cl(2) and eight equivalent Cl(1) atoms to form RbCl12 cuboctahedra that share corners with twelve equivalent Rb(1)Cl12 cuboctahedra, faces with six equivalent Rb(1)Cl12 cuboctahedra, and faces with eight equivalent Cu(1)Cl6 octahedra. All Rb(1)-Cl(2) bond lengths are 3.59 Å. All Rb(1)-Cl(1) bond lengths are 3.48 Å. Cu(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form CuCl6 octahedra that share corners with six equivalent Cu(1)Cl6 octahedra and faces with eight equivalent Rb(1)Cl12 cuboctahedra. The corner-sharing octahedra are not tilted. Both Cu(1)-Cl(2) bond lengths are 2.36 Å. There are two shorter (2.21 Å) and two longer (2.87 Å) Cu(1)-Cl(1) bond lengths. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Rb(1) and two equivalent Cu(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClRb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. In the second Cl site, Cl(2) is bonded in a distorted linear geometry to four equivalent Rb(1) and two equivalent Cu(1) atoms.