KPb2Cl5 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 8-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one Cl(5), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(1), and two equivalent Cl(3) atoms. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Pb(1) and two equivalent Pb(2) atoms to form distorted ClPb4 trigonal pyramids that share corners with four equivalent Cl(2)K2Pb3 trigonal bipyramids, corners with two equivalent Cl(5)K2Pb2 trigonal pyramids, corners with two equivalent Cl(1)Pb4 trigonal pyramids, corners with four equivalent Cl(3)K2Pb2 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb3 trigonal bipyramid,  an edgeedge with one Cl(5)K2Pb2 trigonal pyramid, and  an edgeedge with one Cl(1)Pb4 trigonal pyramid. In the second Cl site, Cl(2) is bonded to two equivalent K(1), one Pb(2), and two equivalent Pb(1) atoms to form distorted ClK2Pb3 trigonal bipyramids that share corners with four equivalent Cl(3)K2Pb2 trigonal pyramids, corners with four equivalent Cl(1)Pb4 trigonal pyramids, corners with five equivalent Cl(5)K2Pb2 trigonal pyramids, edges with two equivalent Cl(2)K2Pb3 trigonal bipyramids,  an edgeedge with one Cl(3)K2Pb2 trigonal pyramid,  an edgeedge with one Cl(5)K2Pb2 trigonal pyramid, and  an edgeedge with one Cl(1)Pb4 trigonal pyramid. In the third Cl site, Cl(3) is bonded to two equivalent K(1) and two equivalent Pb(2) atoms to form distorted ClK2Pb2 trigonal pyramids that share corners with four equivalent Cl(2)K2Pb3 trigonal bipyramids, corners with two equivalent Cl(3)K2Pb2 trigonal pyramids, corners with two equivalent Cl(5)K2Pb2 trigonal pyramids, corners with four equivalent Cl(1)Pb4 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb3 trigonal bipyramid,  an edgeedge with one Cl(3)K2Pb2 trigonal pyramid, and edges with two equivalent Cl(5)K2Pb2 trigonal pyramids. In the fourth Cl site, Cl(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Pb(2), and two equivalent Pb(1) atoms. In the fifth Cl site, Cl(5) is bonded to two equivalent K(1), one Pb(1), and one Pb(2) atom to form ClK2Pb2 trigonal pyramids that share corners with five equivalent Cl(2)K2Pb3 trigonal bipyramids, corners with two equivalent Cl(3)K2Pb2 trigonal pyramids, corners with two equivalent Cl(5)K2Pb2 trigonal pyramids, corners with two equivalent Cl(1)Pb4 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb3 trigonal bipyramid,  an edgeedge with one Cl(1)Pb4 trigonal pyramid, and edges with two equivalent Cl(3)K2Pb2 trigonal pyramids.
KPb2Cl5 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 8-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms. There is one shorter (3.27 Å) and one longer (3.36 Å) K(1)-Cl(2) bond length. There is one shorter (3.20 Å) and one longer (3.29 Å) K(1)-Cl(3) bond length. Both K(1)-Cl(4) bond lengths are 3.26 Å. There is one shorter (3.31 Å) and one longer (3.42 Å) K(1)-Cl(5) bond length. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 7-coordinate geometry to one Cl(5), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms. The Pb(1)-Cl(5) bond length is 2.90 Å. There is one shorter (2.87 Å) and one longer (3.15 Å) Pb(1)-Cl(1) bond length. There is one shorter (2.92 Å) and one longer (3.01 Å) Pb(1)-Cl(2) bond length. There is one shorter (2.97 Å) and one longer (3.24 Å) Pb(1)-Cl(4) bond length. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(1), and two equivalent Cl(3) atoms. The Pb(2)-Cl(2) bond length is 3.16 Å. The Pb(2)-Cl(4) bond length is 3.00 Å. The Pb(2)-Cl(5) bond length is 2.90 Å. There is one shorter (2.96 Å) and one longer (3.00 Å) Pb(2)-Cl(1) bond length. There is one shorter (2.85 Å) and one longer (2.88 Å) Pb(2)-Cl(3) bond length. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Pb(1) and two equivalent Pb(2) atoms to form distorted ClPb4 trigonal pyramids that share corners with four equivalent Cl(2)K2Pb3 trigonal bipyramids, corners with two equivalent Cl(5)K2Pb2 trigonal pyramids, corners with two equivalent Cl(1)Pb4 trigonal pyramids, corners with four equivalent Cl(3)K2Pb2 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb3 trigonal bipyramid,  an edgeedge with one Cl(5)K2Pb2 trigonal pyramid, and  an edgeedge with one Cl(1)Pb4 trigonal pyramid. In the second Cl site, Cl(2) is bonded to two equivalent K(1), one Pb(2), and two equivalent Pb(1) atoms to form distorted ClK2Pb3 trigonal bipyramids that share corners with four equivalent Cl(3)K2Pb2 trigonal pyramids, corners with four equivalent Cl(1)Pb4 trigonal pyramids, corners with five equivalent Cl(5)K2Pb2 trigonal pyramids, edges with two equivalent Cl(2)K2Pb3 trigonal bipyramids,  an edgeedge with one Cl(3)K2Pb2 trigonal pyramid,  an edgeedge with one Cl(5)K2Pb2 trigonal pyramid, and  an edgeedge with one Cl(1)Pb4 trigonal pyramid. In the third Cl site, Cl(3) is bonded to two equivalent K(1) and two equivalent Pb(2) atoms to form distorted ClK2Pb2 trigonal pyramids that share corners with four equivalent Cl(2)K2Pb3 trigonal bipyramids, corners with two equivalent Cl(3)K2Pb2 trigonal pyramids, corners with two equivalent Cl(5)K2Pb2 trigonal pyramids, corners with four equivalent Cl(1)Pb4 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb3 trigonal bipyramid,  an edgeedge with one Cl(3)K2Pb2 trigonal pyramid, and edges with two equivalent Cl(5)K2Pb2 trigonal pyramids. In the fourth Cl site, Cl(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent K(1), one Pb(2), and two equivalent Pb(1) atoms. In the fifth Cl site, Cl(5) is bonded to two equivalent K(1), one Pb(1), and one Pb(2) atom to form ClK2Pb2 trigonal pyramids that share corners with five equivalent Cl(2)K2Pb3 trigonal bipyramids, corners with two equivalent Cl(3)K2Pb2 trigonal pyramids, corners with two equivalent Cl(5)K2Pb2 trigonal pyramids, corners with two equivalent Cl(1)Pb4 trigonal pyramids,  an edgeedge with one Cl(2)K2Pb3 trigonal bipyramid,  an edgeedge with one Cl(1)Pb4 trigonal pyramid, and edges with two equivalent Cl(3)K2Pb2 trigonal pyramids.