RbPbCl3 crystallizes in the monoclinic P2_1 space group. Rb(1) is bonded in a 8-coordinate geometry to two equivalent Cl(3), three equivalent Cl(1), and three equivalent Cl(2) atoms. Pb(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form a mixture of edge and corner-sharing PbCl6 octahedra. The corner-sharing octahedral tilt angles are 42°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to three equivalent Rb(1) and two equivalent Pb(1) atoms to form distorted ClRb3Pb2 trigonal bipyramids that share corners with four equivalent Cl(3)Rb2Pb2 tetrahedra, corners with four equivalent Cl(1)Rb3Pb2 trigonal bipyramids, corners with five equivalent Cl(2)Rb3Pb2 trigonal bipyramids, edges with three equivalent Cl(3)Rb2Pb2 tetrahedra, edges with two equivalent Cl(1)Rb3Pb2 trigonal bipyramids, and edges with four equivalent Cl(2)Rb3Pb2 trigonal bipyramids. In the second Cl site, Cl(2) is bonded to three equivalent Rb(1) and two equivalent Pb(1) atoms to form distorted ClRb3Pb2 trigonal bipyramids that share corners with four equivalent Cl(3)Rb2Pb2 tetrahedra, corners with four equivalent Cl(2)Rb3Pb2 trigonal bipyramids, corners with five equivalent Cl(1)Rb3Pb2 trigonal bipyramids, edges with three equivalent Cl(3)Rb2Pb2 tetrahedra, edges with two equivalent Cl(2)Rb3Pb2 trigonal bipyramids, and edges with four equivalent Cl(1)Rb3Pb2 trigonal bipyramids. In the third Cl site, Cl(3) is bonded to two equivalent Rb(1) and two equivalent Pb(1) atoms to form distorted ClRb2Pb2 tetrahedra that share corners with four equivalent Cl(3)Rb2Pb2 tetrahedra, corners with four equivalent Cl(1)Rb3Pb2 trigonal bipyramids, corners with four equivalent Cl(2)Rb3Pb2 trigonal bipyramids, edges with three equivalent Cl(1)Rb3Pb2 trigonal bipyramids, and edges with three equivalent Cl(2)Rb3Pb2 trigonal bipyramids.
RbPbCl3 crystallizes in the monoclinic P2_1 space group. Rb(1) is bonded in a 8-coordinate geometry to two equivalent Cl(3), three equivalent Cl(1), and three equivalent Cl(2) atoms. There is one shorter (3.26 Å) and one longer (3.27 Å) Rb(1)-Cl(3) bond length. There are two shorter (3.40 Å) and one longer (3.63 Å) Rb(1)-Cl(1) bond length. There are a spread of Rb(1)-Cl(2) bond distances ranging from 3.40-3.62 Å. Pb(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form a mixture of edge and corner-sharing PbCl6 octahedra. The corner-sharing octahedral tilt angles are 42°. There is one shorter (2.92 Å) and one longer (2.93 Å) Pb(1)-Cl(1) bond length. There is one shorter (2.92 Å) and one longer (2.93 Å) Pb(1)-Cl(2) bond length. Both Pb(1)-Cl(3) bond lengths are 2.86 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to three equivalent Rb(1) and two equivalent Pb(1) atoms to form distorted ClRb3Pb2 trigonal bipyramids that share corners with four equivalent Cl(3)Rb2Pb2 tetrahedra, corners with four equivalent Cl(1)Rb3Pb2 trigonal bipyramids, corners with five equivalent Cl(2)Rb3Pb2 trigonal bipyramids, edges with three equivalent Cl(3)Rb2Pb2 tetrahedra, edges with two equivalent Cl(1)Rb3Pb2 trigonal bipyramids, and edges with four equivalent Cl(2)Rb3Pb2 trigonal bipyramids. In the second Cl site, Cl(2) is bonded to three equivalent Rb(1) and two equivalent Pb(1) atoms to form distorted ClRb3Pb2 trigonal bipyramids that share corners with four equivalent Cl(3)Rb2Pb2 tetrahedra, corners with four equivalent Cl(2)Rb3Pb2 trigonal bipyramids, corners with five equivalent Cl(1)Rb3Pb2 trigonal bipyramids, edges with three equivalent Cl(3)Rb2Pb2 tetrahedra, edges with two equivalent Cl(2)Rb3Pb2 trigonal bipyramids, and edges with four equivalent Cl(1)Rb3Pb2 trigonal bipyramids. In the third Cl site, Cl(3) is bonded to two equivalent Rb(1) and two equivalent Pb(1) atoms to form distorted ClRb2Pb2 tetrahedra that share corners with four equivalent Cl(3)Rb2Pb2 tetrahedra, corners with four equivalent Cl(1)Rb3Pb2 trigonal bipyramids, corners with four equivalent Cl(2)Rb3Pb2 trigonal bipyramids, edges with three equivalent Cl(1)Rb3Pb2 trigonal bipyramids, and edges with three equivalent Cl(2)Rb3Pb2 trigonal bipyramids.