RbWCl6 crystallizes in the monoclinic C2/c space group. Rb(1) is bonded to four equivalent Cl(1), four equivalent Cl(2), and four equivalent Cl(3) atoms to form RbCl12 cuboctahedra that share corners with four equivalent Rb(1)Cl12 cuboctahedra, corners with two equivalent W(1)Cl6 octahedra, edges with four equivalent Rb(1)Cl12 cuboctahedra, edges with two equivalent W(1)Cl6 octahedra, and faces with two equivalent W(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 44°. W(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form WCl6 octahedra that share corners with two equivalent Rb(1)Cl12 cuboctahedra, edges with two equivalent Rb(1)Cl12 cuboctahedra, and faces with two equivalent Rb(1)Cl12 cuboctahedra. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one W(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one W(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one W(1) atom.
RbWCl6 crystallizes in the monoclinic C2/c space group. Rb(1) is bonded to four equivalent Cl(1), four equivalent Cl(2), and four equivalent Cl(3) atoms to form RbCl12 cuboctahedra that share corners with four equivalent Rb(1)Cl12 cuboctahedra, corners with two equivalent W(1)Cl6 octahedra, edges with four equivalent Rb(1)Cl12 cuboctahedra, edges with two equivalent W(1)Cl6 octahedra, and faces with two equivalent W(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 44°. There are two shorter (3.65 Å) and two longer (3.69 Å) Rb(1)-Cl(1) bond lengths. There are two shorter (3.51 Å) and two longer (3.55 Å) Rb(1)-Cl(2) bond lengths. There are two shorter (3.55 Å) and two longer (3.57 Å) Rb(1)-Cl(3) bond lengths. W(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form WCl6 octahedra that share corners with two equivalent Rb(1)Cl12 cuboctahedra, edges with two equivalent Rb(1)Cl12 cuboctahedra, and faces with two equivalent Rb(1)Cl12 cuboctahedra. Both W(1)-Cl(1) bond lengths are 2.32 Å. Both W(1)-Cl(2) bond lengths are 2.35 Å. Both W(1)-Cl(3) bond lengths are 2.34 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one W(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one W(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to two equivalent Rb(1) and one W(1) atom.