Rb4PbBr6 crystallizes in the trigonal R-3c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to six equivalent Br(1) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to eight equivalent Br(1) atoms. Pb(1) is bonded in an octahedral geometry to six equivalent Br(1) atoms. Br(1) is bonded to one Rb(1), four equivalent Rb(2), and one Pb(1) atom to form a mixture of corner, face, and edge-sharing BrRb5Pb octahedra. The corner-sharing octahedral tilt angles range from 0-68°.
Rb4PbBr6 crystallizes in the trigonal R-3c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to six equivalent Br(1) atoms. All Rb(1)-Br(1) bond lengths are 3.43 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to eight equivalent Br(1) atoms. There are a spread of Rb(2)-Br(1) bond distances ranging from 3.58-3.73 Å. Pb(1) is bonded in an octahedral geometry to six equivalent Br(1) atoms. All Pb(1)-Br(1) bond lengths are 3.03 Å. Br(1) is bonded to one Rb(1), four equivalent Rb(2), and one Pb(1) atom to form a mixture of corner, face, and edge-sharing BrRb5Pb octahedra. The corner-sharing octahedral tilt angles range from 0-68°.