CsPbCl3 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a body-centered cubic geometry to two equivalent Cl(3), two equivalent Cl(4), and four equivalent Cl(2) atoms. In the second Cs site, Cs(2) is bonded in a distorted body-centered cubic geometry to four equivalent Cl(1) and four equivalent Cl(2) atoms. Pb(1) is bonded to one Cl(3), one Cl(4), two equivalent Cl(1), and two equivalent Cl(2) atoms to form corner-sharing PbCl6 octahedra. The corner-sharing octahedral tilt angles range from 0-27°. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Cs(2) and two equivalent Pb(1) atoms to form distorted ClCs2Pb2 tetrahedra that share corners with four equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(3)Cs2Pb2 tetrahedra, corners with two equivalent Cl(4)Cs2Pb2 tetrahedra, corners with six equivalent Cl(1)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, and  an edgeedge with one Cl(1)Cs2Pb2 tetrahedra. The corner-sharing octahedral tilt angles are 65°. In the second Cl site, Cl(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Pb(1) atoms to form ClCs4Pb2 octahedra that share corners with six equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(3)Cs2Pb2 tetrahedra, corners with two equivalent Cl(4)Cs2Pb2 tetrahedra, corners with four equivalent Cl(1)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, edges with two equivalent Cl(3)Cs2Pb2 tetrahedra, edges with two equivalent Cl(4)Cs2Pb2 tetrahedra, and edges with four equivalent Cl(1)Cs2Pb2 tetrahedra. The corner-sharing octahedra are not tilted. In the third Cl site, Cl(3) is bonded to two equivalent Cs(1) and two equivalent Pb(1) atoms to form distorted ClCs2Pb2 tetrahedra that share corners with four equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(3)Cs2Pb2 tetrahedra, corners with four equivalent Cl(1)Cs2Pb2 tetrahedra, corners with four equivalent Cl(4)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, and  an edgeedge with one Cl(4)Cs2Pb2 tetrahedra. The corner-sharing octahedral tilt angles are 65°. In the fourth Cl site, Cl(4) is bonded to two equivalent Cs(1) and two equivalent Pb(1) atoms to form distorted ClCs2Pb2 tetrahedra that share corners with four equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(4)Cs2Pb2 tetrahedra, corners with four equivalent Cl(1)Cs2Pb2 tetrahedra, corners with four equivalent Cl(3)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, and  an edgeedge with one Cl(3)Cs2Pb2 tetrahedra. The corner-sharing octahedral tilt angles are 65°.
CsPbCl3 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a body-centered cubic geometry to two equivalent Cl(3), two equivalent Cl(4), and four equivalent Cl(2) atoms. Both Cs(1)-Cl(3) bond lengths are 3.58 Å. Both Cs(1)-Cl(4) bond lengths are 3.58 Å. There are two shorter (3.93 Å) and two longer (3.94 Å) Cs(1)-Cl(2) bond lengths. In the second Cs site, Cs(2) is bonded in a distorted body-centered cubic geometry to four equivalent Cl(1) and four equivalent Cl(2) atoms. All Cs(2)-Cl(1) bond lengths are 3.58 Å. There are two shorter (3.92 Å) and two longer (3.95 Å) Cs(2)-Cl(2) bond lengths. Pb(1) is bonded to one Cl(3), one Cl(4), two equivalent Cl(1), and two equivalent Cl(2) atoms to form corner-sharing PbCl6 octahedra. The corner-sharing octahedral tilt angles range from 0-27°. The Pb(1)-Cl(3) bond length is 2.86 Å. The Pb(1)-Cl(4) bond length is 2.86 Å. Both Pb(1)-Cl(1) bond lengths are 2.86 Å. Both Pb(1)-Cl(2) bond lengths are 2.88 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Cs(2) and two equivalent Pb(1) atoms to form distorted ClCs2Pb2 tetrahedra that share corners with four equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(3)Cs2Pb2 tetrahedra, corners with two equivalent Cl(4)Cs2Pb2 tetrahedra, corners with six equivalent Cl(1)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, and  an edgeedge with one Cl(1)Cs2Pb2 tetrahedra. The corner-sharing octahedral tilt angles are 65°. In the second Cl site, Cl(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Pb(1) atoms to form ClCs4Pb2 octahedra that share corners with six equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(3)Cs2Pb2 tetrahedra, corners with two equivalent Cl(4)Cs2Pb2 tetrahedra, corners with four equivalent Cl(1)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, edges with two equivalent Cl(3)Cs2Pb2 tetrahedra, edges with two equivalent Cl(4)Cs2Pb2 tetrahedra, and edges with four equivalent Cl(1)Cs2Pb2 tetrahedra. The corner-sharing octahedra are not tilted. In the third Cl site, Cl(3) is bonded to two equivalent Cs(1) and two equivalent Pb(1) atoms to form distorted ClCs2Pb2 tetrahedra that share corners with four equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(3)Cs2Pb2 tetrahedra, corners with four equivalent Cl(1)Cs2Pb2 tetrahedra, corners with four equivalent Cl(4)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, and  an edgeedge with one Cl(4)Cs2Pb2 tetrahedra. The corner-sharing octahedral tilt angles are 65°. In the fourth Cl site, Cl(4) is bonded to two equivalent Cs(1) and two equivalent Pb(1) atoms to form distorted ClCs2Pb2 tetrahedra that share corners with four equivalent Cl(2)Cs4Pb2 octahedra, corners with two equivalent Cl(4)Cs2Pb2 tetrahedra, corners with four equivalent Cl(1)Cs2Pb2 tetrahedra, corners with four equivalent Cl(3)Cs2Pb2 tetrahedra, edges with four equivalent Cl(2)Cs4Pb2 octahedra, and  an edgeedge with one Cl(3)Cs2Pb2 tetrahedra. The corner-sharing octahedral tilt angles are 65°.