Cs4PbBr6 crystallizes in the trigonal R-3c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to six equivalent Br(1) atoms. In the second Cs site, Cs(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 Cs(1), four equivalent Cs(2), and one Pb(1) atom to form a mixture of corner, edge, and face-sharing BrCs5Pb octahedra. The corner-sharing octahedral tilt angles range from 0-65°.
Cs4PbBr6 crystallizes in the trigonal R-3c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to six equivalent Br(1) atoms. All Cs(1)-Br(1) bond lengths are 3.59 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to eight equivalent Br(1) atoms. There are a spread of Cs(2)-Br(1) bond distances ranging from 3.72-3.84 Å. Pb(1) is bonded in an octahedral geometry to six equivalent Br(1) atoms. All Pb(1)-Br(1) bond lengths are 3.05 Å. Br(1) is bonded to one Cs(1), four equivalent Cs(2), and one Pb(1) atom to form a mixture of corner, edge, and face-sharing BrCs5Pb octahedra. The corner-sharing octahedral tilt angles range from 0-65°.