Rb3Cu2Cl7 crystallizes in the orthorhombic Ccce space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to four equivalent Cl(1) and five equivalent Cl(2) atoms. In the second Rb site, Rb(2) is bonded to four equivalent Cl(3) and eight equivalent Cl(1) atoms to form RbCl12 cuboctahedra that share corners with four equivalent Rb(2)Cl12 cuboctahedra, faces with four equivalent Rb(2)Cl12 cuboctahedra, and faces with eight equivalent Cu(1)Cl6 octahedra. Cu(1) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form CuCl6 octahedra that share corners with five equivalent Cu(1)Cl6 octahedra and faces with four equivalent Rb(2)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Cu(1) atoms to form distorted ClRb4Cu2 octahedra that share corners with six equivalent Cl(2)Rb5Cu octahedra, corners with eight equivalent Cl(1)Rb4Cu2 octahedra, edges with three equivalent Cl(1)Rb4Cu2 octahedra, faces with two equivalent Cl(2)Rb5Cu octahedra, and faces with four equivalent Cl(1)Rb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-72°. In the second Cl site, Cl(2) is bonded to five equivalent Rb(1) and one Cu(1) atom to form distorted ClRb5Cu octahedra that share corners with four equivalent Cl(2)Rb5Cu octahedra, corners with twelve equivalent Cl(1)Rb4Cu2 octahedra, edges with eight equivalent Cl(2)Rb5Cu octahedra, and faces with four equivalent Cl(1)Rb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 8-59°. In the third Cl site, Cl(3) is bonded in a distorted linear geometry to four equivalent Rb(2) and two equivalent Cu(1) atoms.
Rb3Cu2Cl7 crystallizes in the orthorhombic Ccce space group. There are two inequivalent Rb sites. In the first Rb site, 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 is one shorter (3.30 Å) and four longer (3.59 Å) Rb(1)-Cl(2) bond lengths. In the second Rb site, Rb(2) is bonded to four equivalent Cl(3) and eight equivalent Cl(1) atoms to form RbCl12 cuboctahedra that share corners with four equivalent Rb(2)Cl12 cuboctahedra, faces with four equivalent Rb(2)Cl12 cuboctahedra, and faces with eight equivalent Cu(1)Cl6 octahedra. All Rb(2)-Cl(3) bond lengths are 3.58 Å. There are four shorter (3.42 Å) and four longer (3.43 Å) Rb(2)-Cl(1) bond lengths. Cu(1) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form CuCl6 octahedra that share corners with five equivalent Cu(1)Cl6 octahedra and faces with four equivalent Rb(2)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. The Cu(1)-Cl(2) bond length is 2.36 Å. The Cu(1)-Cl(3) bond length is 2.35 Å. There are two shorter (2.23 Å) and two longer (2.83 Å) Cu(1)-Cl(1) bond lengths. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Cu(1) atoms to form distorted ClRb4Cu2 octahedra that share corners with six equivalent Cl(2)Rb5Cu octahedra, corners with eight equivalent Cl(1)Rb4Cu2 octahedra, edges with three equivalent Cl(1)Rb4Cu2 octahedra, faces with two equivalent Cl(2)Rb5Cu octahedra, and faces with four equivalent Cl(1)Rb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-72°. In the second Cl site, Cl(2) is bonded to five equivalent Rb(1) and one Cu(1) atom to form distorted ClRb5Cu octahedra that share corners with four equivalent Cl(2)Rb5Cu octahedra, corners with twelve equivalent Cl(1)Rb4Cu2 octahedra, edges with eight equivalent Cl(2)Rb5Cu octahedra, and faces with four equivalent Cl(1)Rb4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 8-59°. In the third Cl site, Cl(3) is bonded in a distorted linear geometry to four equivalent Rb(2) and two equivalent Cu(1) atoms.