Rb3Mn2Br7 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 Br(1) and five equivalent Br(2) atoms. In the second Rb site, Rb(2) is bonded to four equivalent Br(3) and eight equivalent Br(1) atoms to form RbBr12 cuboctahedra that share corners with four equivalent Rb(2)Br12 cuboctahedra, faces with four equivalent Rb(2)Br12 cuboctahedra, and faces with eight equivalent Mn(1)Br6 octahedra. Mn(1) is bonded to one Br(2), one Br(3), and four equivalent Br(1) atoms to form MnBr6 octahedra that share corners with five equivalent Mn(1)Br6 octahedra and faces with four equivalent Rb(2)Br12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Mn(1) atoms to form distorted BrRb4Mn2 octahedra that share corners with four equivalent Br(3)Rb4Mn2 octahedra, corners with six equivalent Br(2)Rb5Mn octahedra, corners with eight equivalent Br(1)Rb4Mn2 octahedra, edges with three equivalent Br(1)Rb4Mn2 octahedra, faces with two equivalent Br(3)Rb4Mn2 octahedra, faces with two equivalent Br(2)Rb5Mn octahedra, and faces with four equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second Br site, Br(2) is bonded to five equivalent Rb(1) and one Mn(1) atom to form distorted BrRb5Mn octahedra that share  a cornercorner with one Br(3)Rb4Mn2 octahedra, corners with four equivalent Br(2)Rb5Mn octahedra, corners with twelve equivalent Br(1)Rb4Mn2 octahedra, edges with eight equivalent Br(2)Rb5Mn octahedra, and faces with four equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-53°. In the third Br site, Br(3) is bonded to four equivalent Rb(2) and two equivalent Mn(1) atoms to form distorted BrRb4Mn2 octahedra that share corners with two equivalent Br(2)Rb5Mn octahedra, corners with four equivalent Br(3)Rb4Mn2 octahedra, corners with sixteen equivalent Br(1)Rb4Mn2 octahedra, edges with four equivalent Br(3)Rb4Mn2 octahedra, and faces with eight equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the fourth Br site, Br(3) is bonded to four equivalent Rb(2) and two equivalent Mn(1) atoms to form distorted BrRb4Mn2 octahedra that share corners with two equivalent Br(2)Rb5Mn octahedra, corners with four equivalent Br(3)Rb4Mn2 octahedra, corners with sixteen equivalent Br(1)Rb4Mn2 octahedra, edges with four equivalent Br(3)Rb4Mn2 octahedra, and faces with eight equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°.
Rb3Mn2Br7 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 Br(1) and five equivalent Br(2) atoms. All Rb(1)-Br(1) bond lengths are 3.59 Å. There is one shorter (3.47 Å) and four longer (3.84 Å) Rb(1)-Br(2) bond lengths. In the second Rb site, Rb(2) is bonded to four equivalent Br(3) and eight equivalent Br(1) atoms to form RbBr12 cuboctahedra that share corners with four equivalent Rb(2)Br12 cuboctahedra, faces with four equivalent Rb(2)Br12 cuboctahedra, and faces with eight equivalent Mn(1)Br6 octahedra. All Rb(2)-Br(3) bond lengths are 3.82 Å. All Rb(2)-Br(1) bond lengths are 3.80 Å. Mn(1) is bonded to one Br(2), one Br(3), and four equivalent Br(1) atoms to form MnBr6 octahedra that share corners with five equivalent Mn(1)Br6 octahedra and faces with four equivalent Rb(2)Br12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-5°. The Mn(1)-Br(2) bond length is 2.63 Å. The Mn(1)-Br(3) bond length is 2.78 Å. All Mn(1)-Br(1) bond lengths are 2.71 Å. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Mn(1) atoms to form distorted BrRb4Mn2 octahedra that share corners with four equivalent Br(3)Rb4Mn2 octahedra, corners with six equivalent Br(2)Rb5Mn octahedra, corners with eight equivalent Br(1)Rb4Mn2 octahedra, edges with three equivalent Br(1)Rb4Mn2 octahedra, faces with two equivalent Br(3)Rb4Mn2 octahedra, faces with two equivalent Br(2)Rb5Mn octahedra, and faces with four equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second Br site, Br(2) is bonded to five equivalent Rb(1) and one Mn(1) atom to form distorted BrRb5Mn octahedra that share  a cornercorner with one Br(3)Rb4Mn2 octahedra, corners with four equivalent Br(2)Rb5Mn octahedra, corners with twelve equivalent Br(1)Rb4Mn2 octahedra, edges with eight equivalent Br(2)Rb5Mn octahedra, and faces with four equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-53°. In the third Br site, Br(3) is bonded to four equivalent Rb(2) and two equivalent Mn(1) atoms to form distorted BrRb4Mn2 octahedra that share corners with two equivalent Br(2)Rb5Mn octahedra, corners with four equivalent Br(3)Rb4Mn2 octahedra, corners with sixteen equivalent Br(1)Rb4Mn2 octahedra, edges with four equivalent Br(3)Rb4Mn2 octahedra, and faces with eight equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. Both Br(3)-Mn(1) bond lengths are 2.78 Å. In the fourth Br site, Br(3) is bonded to four equivalent Rb(2) and two equivalent Mn(1) atoms to form distorted BrRb4Mn2 octahedra that share corners with two equivalent Br(2)Rb5Mn octahedra, corners with four equivalent Br(3)Rb4Mn2 octahedra, corners with sixteen equivalent Br(1)Rb4Mn2 octahedra, edges with four equivalent Br(3)Rb4Mn2 octahedra, and faces with eight equivalent Br(1)Rb4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. All Br(3)-Rb(2) bond lengths are 3.82 Å.