KPb2Cl5 crystallizes in the orthorhombic Pna2_1 space group. K(1) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(4), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(5) atoms. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a distorted pentagonal planar geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom. In the second Pb site, Pb(2) is bonded to one Cl(1), one Cl(2), one Cl(5), two equivalent Cl(3), and two equivalent Cl(4) atoms to form distorted edge-sharing PbCl7 pentagonal bipyramids. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Pb(1), and one Pb(2) atom. In the second Cl site, Cl(2) is bonded to two equivalent K(1), one Pb(1), and one Pb(2) atom to form ClK2Pb2 trigonal pyramids that share  a cornercorner with one Cl(3)KPb3 trigonal pyramid, corners with two equivalent Cl(2)K2Pb2 trigonal pyramids, corners with three equivalent Cl(4)KPb3 trigonal pyramids,  an edgeedge with one Cl(4)KPb3 trigonal pyramid, and edges with two equivalent Cl(3)KPb3 trigonal pyramids. In the third Cl site, Cl(3) is bonded to one K(1), one Pb(1), and two equivalent Pb(2) atoms to form ClKPb3 trigonal pyramids that share  a cornercorner with one Cl(2)K2Pb2 trigonal pyramid, corners with two equivalent Cl(3)KPb3 trigonal pyramids, corners with four equivalent Cl(4)KPb3 trigonal pyramids,  an edgeedge with one Cl(4)KPb3 trigonal pyramid, and edges with two equivalent Cl(2)K2Pb2 trigonal pyramids. In the fourth Cl site, Cl(4) is bonded to one K(1), one Pb(1), and two equivalent Pb(2) atoms to form distorted ClKPb3 trigonal pyramids that share corners with two equivalent Cl(4)KPb3 trigonal pyramids, corners with three equivalent Cl(2)K2Pb2 trigonal pyramids, corners with four equivalent Cl(3)KPb3 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb2 trigonal pyramid, and  an edgeedge with one Cl(3)KPb3 trigonal pyramid. In the fifth Cl site, Cl(5) is bonded in a see-saw-like geometry to two equivalent K(1), one Pb(1), and one Pb(2) atom.
KPb2Cl5 crystallizes in the orthorhombic Pna2_1 space group. K(1) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(4), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(5) atoms. The K(1)-Cl(3) bond length is 3.22 Å. The K(1)-Cl(4) bond length is 3.19 Å. There is one shorter (3.11 Å) and one longer (3.13 Å) K(1)-Cl(1) bond length. There is one shorter (3.28 Å) and one longer (3.33 Å) K(1)-Cl(2) bond length. There is one shorter (3.15 Å) and one longer (3.22 Å) K(1)-Cl(5) bond length. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a distorted pentagonal planar geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom. The Pb(1)-Cl(1) bond length is 3.02 Å. The Pb(1)-Cl(2) bond length is 2.76 Å. The Pb(1)-Cl(3) bond length is 2.85 Å. The Pb(1)-Cl(4) bond length is 3.07 Å. The Pb(1)-Cl(5) bond length is 2.94 Å. In the second Pb site, Pb(2) is bonded to one Cl(1), one Cl(2), one Cl(5), two equivalent Cl(3), and two equivalent Cl(4) atoms to form distorted edge-sharing PbCl7 pentagonal bipyramids. The Pb(2)-Cl(1) bond length is 3.02 Å. The Pb(2)-Cl(2) bond length is 2.98 Å. The Pb(2)-Cl(5) bond length is 2.96 Å. There is one shorter (2.89 Å) and one longer (3.02 Å) Pb(2)-Cl(3) bond length. There is one shorter (2.91 Å) and one longer (2.95 Å) Pb(2)-Cl(4) bond length. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Pb(1), and one Pb(2) atom. In the second Cl site, Cl(2) is bonded to two equivalent K(1), one Pb(1), and one Pb(2) atom to form ClK2Pb2 trigonal pyramids that share  a cornercorner with one Cl(3)KPb3 trigonal pyramid, corners with two equivalent Cl(2)K2Pb2 trigonal pyramids, corners with three equivalent Cl(4)KPb3 trigonal pyramids,  an edgeedge with one Cl(4)KPb3 trigonal pyramid, and edges with two equivalent Cl(3)KPb3 trigonal pyramids. In the third Cl site, Cl(3) is bonded to one K(1), one Pb(1), and two equivalent Pb(2) atoms to form ClKPb3 trigonal pyramids that share  a cornercorner with one Cl(2)K2Pb2 trigonal pyramid, corners with two equivalent Cl(3)KPb3 trigonal pyramids, corners with four equivalent Cl(4)KPb3 trigonal pyramids,  an edgeedge with one Cl(4)KPb3 trigonal pyramid, and edges with two equivalent Cl(2)K2Pb2 trigonal pyramids. In the fourth Cl site, Cl(4) is bonded to one K(1), one Pb(1), and two equivalent Pb(2) atoms to form distorted ClKPb3 trigonal pyramids that share corners with two equivalent Cl(4)KPb3 trigonal pyramids, corners with three equivalent Cl(2)K2Pb2 trigonal pyramids, corners with four equivalent Cl(3)KPb3 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb2 trigonal pyramid, and  an edgeedge with one Cl(3)KPb3 trigonal pyramid. In the fifth Cl site, Cl(5) is bonded in a see-saw-like geometry to two equivalent K(1), one Pb(1), and one Pb(2) atom.