CsPb2Cl5 crystallizes in the triclinic P1 space group. Cs(1) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), one Cl(5), and two equivalent Cl(3) atoms. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form a mixture of distorted edge, face, and corner-sharing PbCl5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 66°. In the second Pb site, Pb(2) is bonded to one Cl(1), one Cl(3), one Cl(4), one Cl(5), and two equivalent Cl(2) atoms to form PbCl6 octahedra that share corners with two equivalent Pb(2)Cl6 octahedra,  a cornercorner with one Pb(1)Cl5 trigonal bipyramid,  an edgeedge with one Pb(1)Cl5 trigonal bipyramid, and  a faceface with one Pb(1)Cl5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 18°. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to one Cs(1), one Pb(1), and one Pb(2) atom. In the second Cl site, Cl(2) is bonded in a distorted see-saw-like geometry to one Cs(1), one Pb(1), and two equivalent Pb(2) atoms. In the third Cl site, Cl(3) is bonded to two equivalent Cs(1), one Pb(1), and one Pb(2) atom to form corner-sharing ClCs2Pb2 trigonal pyramids. In the fourth Cl site, Cl(4) is bonded in a T-shaped geometry to one Cs(1), one Pb(1), and one Pb(2) atom. In the fifth Cl site, Cl(5) is bonded in a T-shaped geometry to one Cs(1), one Pb(1), and one Pb(2) atom.
CsPb2Cl5 crystallizes in the triclinic P1 space group. Cs(1) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), one Cl(5), and two equivalent Cl(3) atoms. The Cs(1)-Cl(1) bond length is 4.01 Å. The Cs(1)-Cl(2) bond length is 3.55 Å. The Cs(1)-Cl(4) bond length is 3.46 Å. The Cs(1)-Cl(5) bond length is 3.46 Å. There is one shorter (3.60 Å) and one longer (3.67 Å) Cs(1)-Cl(3) bond length. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form a mixture of distorted edge, face, and corner-sharing PbCl5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 66°. The Pb(1)-Cl(1) bond length is 2.76 Å. The Pb(1)-Cl(2) bond length is 2.99 Å. The Pb(1)-Cl(3) bond length is 2.96 Å. The Pb(1)-Cl(4) bond length is 2.79 Å. The Pb(1)-Cl(5) bond length is 2.95 Å. In the second Pb site, Pb(2) is bonded to one Cl(1), one Cl(3), one Cl(4), one Cl(5), and two equivalent Cl(2) atoms to form PbCl6 octahedra that share corners with two equivalent Pb(2)Cl6 octahedra,  a cornercorner with one Pb(1)Cl5 trigonal bipyramid,  an edgeedge with one Pb(1)Cl5 trigonal bipyramid, and  a faceface with one Pb(1)Cl5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 18°. The Pb(2)-Cl(1) bond length is 2.99 Å. The Pb(2)-Cl(3) bond length is 2.91 Å. The Pb(2)-Cl(4) bond length is 2.92 Å. The Pb(2)-Cl(5) bond length is 2.82 Å. There is one shorter (2.80 Å) and one longer (3.05 Å) Pb(2)-Cl(2) bond length. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to one Cs(1), one Pb(1), and one Pb(2) atom. In the second Cl site, Cl(2) is bonded in a distorted see-saw-like geometry to one Cs(1), one Pb(1), and two equivalent Pb(2) atoms. In the third Cl site, Cl(3) is bonded to two equivalent Cs(1), one Pb(1), and one Pb(2) atom to form corner-sharing ClCs2Pb2 trigonal pyramids. In the fourth Cl site, Cl(4) is bonded in a T-shaped geometry to one Cs(1), one Pb(1), and one Pb(2) atom. In the fifth Cl site, Cl(5) is bonded in a T-shaped geometry to one Cs(1), one Pb(1), and one Pb(2) atom.