Rb2PbCl5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), and three equivalent Cl(5) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(4), two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(5) atoms. Pb(1) is bonded to one Cl(2), one Cl(3), two equivalent Cl(1), and two equivalent Cl(4) atoms to form a mixture of distorted corner and edge-sharing PbCl6 pentagonal pyramids. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Rb(2) and two equivalent Pb(1) atoms to form distorted ClRb2Pb2 trigonal pyramids that share corners with four equivalent Cl(5)Rb5 trigonal bipyramids, corners with two equivalent Cl(1)Rb2Pb2 trigonal pyramids, and  an edgeedge with one Cl(1)Rb2Pb2 trigonal pyramid. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Rb(2), two equivalent Rb(1), and one Pb(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Pb(1) atom. In the fourth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Rb(2) and two equivalent Pb(1) atoms. In the fifth Cl site, Cl(5) is bonded to two equivalent Rb(2) and three equivalent Rb(1) atoms to form ClRb5 trigonal bipyramids that share corners with four equivalent Cl(5)Rb5 trigonal bipyramids, corners with four equivalent Cl(1)Rb2Pb2 trigonal pyramids, and edges with two equivalent Cl(5)Rb5 trigonal bipyramids.
Rb2PbCl5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), and three equivalent Cl(5) atoms. There is one shorter (3.57 Å) and one longer (3.66 Å) Rb(1)-Cl(2) bond length. There is one shorter (3.35 Å) and one longer (3.91 Å) Rb(1)-Cl(3) bond length. There are a spread of Rb(1)-Cl(5) bond distances ranging from 3.43-3.65 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(4), two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(5) atoms. The Rb(2)-Cl(2) bond length is 3.20 Å. The Rb(2)-Cl(4) bond length is 3.59 Å. Both Rb(2)-Cl(1) bond lengths are 3.34 Å. There is one shorter (3.31 Å) and one longer (3.78 Å) Rb(2)-Cl(3) bond length. There is one shorter (3.16 Å) and one longer (3.45 Å) Rb(2)-Cl(5) bond length. Pb(1) is bonded to one Cl(2), one Cl(3), two equivalent Cl(1), and two equivalent Cl(4) atoms to form a mixture of distorted corner and edge-sharing PbCl6 pentagonal pyramids. The Pb(1)-Cl(2) bond length is 2.63 Å. The Pb(1)-Cl(3) bond length is 2.76 Å. There is one shorter (2.69 Å) and one longer (3.04 Å) Pb(1)-Cl(1) bond length. There is one shorter (2.78 Å) and one longer (3.04 Å) Pb(1)-Cl(4) bond length. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Rb(2) and two equivalent Pb(1) atoms to form distorted ClRb2Pb2 trigonal pyramids that share corners with four equivalent Cl(5)Rb5 trigonal bipyramids, corners with two equivalent Cl(1)Rb2Pb2 trigonal pyramids, and  an edgeedge with one Cl(1)Rb2Pb2 trigonal pyramid. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Rb(2), two equivalent Rb(1), and one Pb(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Pb(1) atom. In the fourth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Rb(2) and two equivalent Pb(1) atoms. In the fifth Cl site, Cl(5) is bonded to two equivalent Rb(2) and three equivalent Rb(1) atoms to form ClRb5 trigonal bipyramids that share corners with four equivalent Cl(5)Rb5 trigonal bipyramids, corners with four equivalent Cl(1)Rb2Pb2 trigonal pyramids, and edges with two equivalent Cl(5)Rb5 trigonal bipyramids.