Cs2Pb(ICl)2 is (La,Ba)CuO4-derived structured and crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded in a 9-coordinate geometry to five equivalent I(1) and four equivalent Cl(1) atoms. Pb(1) is bonded to two equivalent I(1) and four equivalent Cl(1) atoms to form corner-sharing PbI2Cl4 octahedra. The corner-sharing octahedra are not tilted. I(1) is bonded to five equivalent Cs(1) and one Pb(1) atom to form ICs5Pb octahedra that share corners with five equivalent I(1)Cs5Pb octahedra, corners with twelve equivalent Cl(1)Cs4Pb2 octahedra, edges with eight equivalent I(1)Cs5Pb octahedra, and faces with four equivalent Cl(1)Cs4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-51°. Cl(1) is bonded to four equivalent Cs(1) and two equivalent Pb(1) atoms to form ClCs4Pb2 octahedra that share corners with two equivalent Cl(1)Cs4Pb2 octahedra, corners with twelve equivalent I(1)Cs5Pb octahedra, edges with two equivalent Cl(1)Cs4Pb2 octahedra, faces with four equivalent I(1)Cs5Pb octahedra, and faces with four equivalent Cl(1)Cs4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-51°.
Cs2Pb(ICl)2 is (La,Ba)CuO4-derived structured and crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded in a 9-coordinate geometry to five equivalent I(1) and four equivalent Cl(1) atoms. There is one shorter (3.94 Å) and four longer (4.13 Å) Cs(1)-I(1) bond lengths. All Cs(1)-Cl(1) bond lengths are 3.86 Å. Pb(1) is bonded to two equivalent I(1) and four equivalent Cl(1) atoms to form corner-sharing PbI2Cl4 octahedra. The corner-sharing octahedra are not tilted. Both Pb(1)-I(1) bond lengths are 3.24 Å. All Pb(1)-Cl(1) bond lengths are 2.88 Å. I(1) is bonded to five equivalent Cs(1) and one Pb(1) atom to form ICs5Pb octahedra that share corners with five equivalent I(1)Cs5Pb octahedra, corners with twelve equivalent Cl(1)Cs4Pb2 octahedra, edges with eight equivalent I(1)Cs5Pb octahedra, and faces with four equivalent Cl(1)Cs4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-51°. Cl(1) is bonded to four equivalent Cs(1) and two equivalent Pb(1) atoms to form ClCs4Pb2 octahedra that share corners with two equivalent Cl(1)Cs4Pb2 octahedra, corners with twelve equivalent I(1)Cs5Pb octahedra, edges with two equivalent Cl(1)Cs4Pb2 octahedra, faces with four equivalent I(1)Cs5Pb octahedra, and faces with four equivalent Cl(1)Cs4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 0-51°.