Rb3Mn2Cl7 crystallizes in the tetragonal I4/mmm 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 Mn(1)Cl6 octahedra. Mn(1) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form MnCl6 octahedra that share corners with five equivalent Mn(1)Cl6 octahedra and faces with four equivalent Rb(2)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-4°. 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 Mn(1) atoms to form distorted ClRb4Mn2 octahedra that share corners with four equivalent Cl(3)Rb4Mn2 octahedra, corners with six equivalent Cl(2)Rb5Mn octahedra, corners with eight equivalent Cl(1)Rb4Mn2 octahedra, edges with three equivalent Cl(1)Rb4Mn2 octahedra, faces with two equivalent Cl(3)Rb4Mn2 octahedra, faces with two equivalent Cl(2)Rb5Mn octahedra, and faces with four equivalent Cl(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-61°. In the second Cl site, Cl(2) is bonded to five equivalent Rb(1) and one Mn(1) atom to form distorted ClRb5Mn octahedra that share  a cornercorner with one Cl(3)Rb4Mn2 octahedra, corners with four equivalent Cl(2)Rb5Mn octahedra, corners with twelve equivalent Cl(1)Rb4Mn2 octahedra, edges with eight equivalent Cl(2)Rb5Mn octahedra, and faces with four equivalent Cl(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-55°. In the third Cl site, Cl(3) is bonded to four equivalent Rb(2) and two equivalent Mn(1) atoms to form distorted ClRb4Mn2 octahedra that share corners with two equivalent Cl(2)Rb5Mn octahedra, corners with four equivalent Cl(3)Rb4Mn2 octahedra, corners with sixteen equivalent Cl(1)Rb4Mn2 octahedra, edges with four equivalent Cl(3)Rb4Mn2 octahedra, and faces with eight equivalent Cl(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°.
Rb3Mn2Cl7 crystallizes in the tetragonal I4/mmm 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 3.40 Å. There is one shorter (3.28 Å) and four longer (3.58 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 Mn(1)Cl6 octahedra. All Rb(2)-Cl(3) bond lengths are 3.57 Å. All Rb(2)-Cl(1) bond lengths are 3.54 Å. Mn(1) is bonded to one Cl(2), one Cl(3), and four equivalent Cl(1) atoms to form MnCl6 octahedra that share corners with five equivalent Mn(1)Cl6 octahedra and faces with four equivalent Rb(2)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-4°. The Mn(1)-Cl(2) bond length is 2.49 Å. The Mn(1)-Cl(3) bond length is 2.57 Å. All Mn(1)-Cl(1) bond lengths are 2.53 Å. 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 Mn(1) atoms to form distorted ClRb4Mn2 octahedra that share corners with four equivalent Cl(3)Rb4Mn2 octahedra, corners with six equivalent Cl(2)Rb5Mn octahedra, corners with eight equivalent Cl(1)Rb4Mn2 octahedra, edges with three equivalent Cl(1)Rb4Mn2 octahedra, faces with two equivalent Cl(3)Rb4Mn2 octahedra, faces with two equivalent Cl(2)Rb5Mn octahedra, and faces with four equivalent Cl(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-61°. In the second Cl site, Cl(2) is bonded to five equivalent Rb(1) and one Mn(1) atom to form distorted ClRb5Mn octahedra that share  a cornercorner with one Cl(3)Rb4Mn2 octahedra, corners with four equivalent Cl(2)Rb5Mn octahedra, corners with twelve equivalent Cl(1)Rb4Mn2 octahedra, edges with eight equivalent Cl(2)Rb5Mn octahedra, and faces with four equivalent Cl(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-55°. In the third Cl site, Cl(3) is bonded to four equivalent Rb(2) and two equivalent Mn(1) atoms to form distorted ClRb4Mn2 octahedra that share corners with two equivalent Cl(2)Rb5Mn octahedra, corners with four equivalent Cl(3)Rb4Mn2 octahedra, corners with sixteen equivalent Cl(1)Rb4Mn2 octahedra, edges with four equivalent Cl(3)Rb4Mn2 octahedra, and faces with eight equivalent Cl(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°.