Cs4PbI6 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 I(1) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to eight equivalent I(1) atoms. Pb(1) is bonded in an octahedral geometry to six equivalent I(1) atoms. I(1) is bonded to one Cs(1), four equivalent Cs(2), and one Pb(1) atom to form a mixture of face, corner, and edge-sharing ICs5Pb octahedra. The corner-sharing octahedral tilt angles range from 0-66°.
Cs4PbI6 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 I(1) atoms. All Cs(1)-I(1) bond lengths are 3.82 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to eight equivalent I(1) atoms. There are a spread of Cs(2)-I(1) bond distances ranging from 3.95-4.09 Å. Pb(1) is bonded in an octahedral geometry to six equivalent I(1) atoms. All Pb(1)-I(1) bond lengths are 3.26 Å. I(1) is bonded to one Cs(1), four equivalent Cs(2), and one Pb(1) atom to form a mixture of face, corner, and edge-sharing ICs5Pb octahedra. The corner-sharing octahedral tilt angles range from 0-66°.