Rb2Pb4O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(7), and two equivalent O(4) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(7), and two equivalent O(3) atoms. There are four inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form edge-sharing PbO6 octahedra. In the second Pb site, Pb(2) is bonded to one O(2), one O(3), one O(4), one O(6), and two equivalent O(1) atoms to form edge-sharing PbO6 octahedra. In the third Pb site, Pb(3) is bonded in a 3-coordinate geometry to one O(5), one O(6), and one O(7) atom. In the fourth Pb site, Pb(4) is bonded in a distorted T-shaped geometry to one O(5), one O(6), and one O(7) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), one Rb(2), one Pb(1), and two equivalent Pb(2) atoms to form distorted ORb2Pb3 trigonal bipyramids that share corners with four equivalent O(4)Rb3Pb2 square pyramids,  an edgeedge with one O(4)Rb3Pb2 square pyramid, edges with three equivalent O(3)Rb3Pb2 square pyramids,  an edgeedge with one O(7)Rb2Pb2 tetrahedra,  an edgeedge with one O(1)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(2)Rb2Pb3 trigonal bipyramids. In the second O site, O(2) is bonded to one Rb(1), one Rb(2), one Pb(2), and two equivalent Pb(1) atoms to form distorted ORb2Pb3 trigonal bipyramids that share corners with four equivalent O(3)Rb3Pb2 square pyramids, corners with two equivalent O(7)Rb2Pb2 tetrahedra,  an edgeedge with one O(3)Rb3Pb2 square pyramid, edges with three equivalent O(4)Rb3Pb2 square pyramids,  an edgeedge with one O(2)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(1)Rb2Pb3 trigonal bipyramids. In the third O site, O(3) is bonded to one Rb(1), two equivalent Rb(2), one Pb(1), and one Pb(2) atom to form distorted ORb3Pb2 square pyramids that share  a cornercorner with one O(7)Rb2Pb2 tetrahedra, corners with four equivalent O(2)Rb2Pb3 trigonal bipyramids,  an edgeedge with one O(3)Rb3Pb2 square pyramid, edges with three equivalent O(4)Rb3Pb2 square pyramids,  an edgeedge with one O(7)Rb2Pb2 tetrahedra,  an edgeedge with one O(2)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(1)Rb2Pb3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Rb(2), two equivalent Rb(1), one Pb(1), and one Pb(2) atom to form distorted ORb3Pb2 square pyramids that share corners with three equivalent O(7)Rb2Pb2 tetrahedra, corners with four equivalent O(1)Rb2Pb3 trigonal bipyramids,  an edgeedge with one O(4)Rb3Pb2 square pyramid, edges with three equivalent O(3)Rb3Pb2 square pyramids,  an edgeedge with one O(1)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(2)Rb2Pb3 trigonal bipyramids. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Pb(1), one Pb(3), and one Pb(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Pb(2), one Pb(3), and one Pb(4) atom. In the seventh O site, O(7) is bonded to one Rb(1), one Rb(2), one Pb(3), and one Pb(4) atom to form distorted ORb2Pb2 tetrahedra that share  a cornercorner with one O(3)Rb3Pb2 square pyramid, corners with three equivalent O(4)Rb3Pb2 square pyramids, corners with two equivalent O(2)Rb2Pb3 trigonal bipyramids,  an edgeedge with one O(3)Rb3Pb2 square pyramid, and  an edgeedge with one O(1)Rb2Pb3 trigonal bipyramid.
Rb2Pb4O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(7), and two equivalent O(4) atoms. The Rb(1)-O(1) bond length is 2.87 Å. The Rb(1)-O(2) bond length is 2.89 Å. The Rb(1)-O(3) bond length is 2.92 Å. The Rb(1)-O(7) bond length is 2.81 Å. There is one shorter (2.92 Å) and one longer (3.31 Å) Rb(1)-O(4) bond length. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(7), and two equivalent O(3) atoms. The Rb(2)-O(1) bond length is 2.87 Å. The Rb(2)-O(2) bond length is 2.90 Å. The Rb(2)-O(4) bond length is 2.92 Å. The Rb(2)-O(7) bond length is 2.83 Å. There is one shorter (2.92 Å) and one longer (3.15 Å) Rb(2)-O(3) bond length. There are four inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form edge-sharing PbO6 octahedra. The Pb(1)-O(1) bond length is 2.26 Å. The Pb(1)-O(3) bond length is 2.17 Å. The Pb(1)-O(4) bond length is 2.18 Å. The Pb(1)-O(5) bond length is 2.15 Å. There is one shorter (2.23 Å) and one longer (2.28 Å) Pb(1)-O(2) bond length. In the second Pb site, Pb(2) is bonded to one O(2), one O(3), one O(4), one O(6), and two equivalent O(1) atoms to form edge-sharing PbO6 octahedra. The Pb(2)-O(2) bond length is 2.28 Å. The Pb(2)-O(3) bond length is 2.17 Å. The Pb(2)-O(4) bond length is 2.18 Å. The Pb(2)-O(6) bond length is 2.15 Å. There is one shorter (2.24 Å) and one longer (2.27 Å) Pb(2)-O(1) bond length. In the third Pb site, Pb(3) is bonded in a 3-coordinate geometry to one O(5), one O(6), and one O(7) atom. The Pb(3)-O(5) bond length is 2.27 Å. The Pb(3)-O(6) bond length is 2.27 Å. The Pb(3)-O(7) bond length is 2.16 Å. In the fourth Pb site, Pb(4) is bonded in a distorted T-shaped geometry to one O(5), one O(6), and one O(7) atom. The Pb(4)-O(5) bond length is 2.26 Å. The Pb(4)-O(6) bond length is 2.26 Å. The Pb(4)-O(7) bond length is 2.16 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), one Rb(2), one Pb(1), and two equivalent Pb(2) atoms to form distorted ORb2Pb3 trigonal bipyramids that share corners with four equivalent O(4)Rb3Pb2 square pyramids,  an edgeedge with one O(4)Rb3Pb2 square pyramid, edges with three equivalent O(3)Rb3Pb2 square pyramids,  an edgeedge with one O(7)Rb2Pb2 tetrahedra,  an edgeedge with one O(1)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(2)Rb2Pb3 trigonal bipyramids. In the second O site, O(2) is bonded to one Rb(1), one Rb(2), one Pb(2), and two equivalent Pb(1) atoms to form distorted ORb2Pb3 trigonal bipyramids that share corners with four equivalent O(3)Rb3Pb2 square pyramids, corners with two equivalent O(7)Rb2Pb2 tetrahedra,  an edgeedge with one O(3)Rb3Pb2 square pyramid, edges with three equivalent O(4)Rb3Pb2 square pyramids,  an edgeedge with one O(2)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(1)Rb2Pb3 trigonal bipyramids. In the third O site, O(3) is bonded to one Rb(1), two equivalent Rb(2), one Pb(1), and one Pb(2) atom to form distorted ORb3Pb2 square pyramids that share  a cornercorner with one O(7)Rb2Pb2 tetrahedra, corners with four equivalent O(2)Rb2Pb3 trigonal bipyramids,  an edgeedge with one O(3)Rb3Pb2 square pyramid, edges with three equivalent O(4)Rb3Pb2 square pyramids,  an edgeedge with one O(7)Rb2Pb2 tetrahedra,  an edgeedge with one O(2)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(1)Rb2Pb3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Rb(2), two equivalent Rb(1), one Pb(1), and one Pb(2) atom to form distorted ORb3Pb2 square pyramids that share corners with three equivalent O(7)Rb2Pb2 tetrahedra, corners with four equivalent O(1)Rb2Pb3 trigonal bipyramids,  an edgeedge with one O(4)Rb3Pb2 square pyramid, edges with three equivalent O(3)Rb3Pb2 square pyramids,  an edgeedge with one O(1)Rb2Pb3 trigonal bipyramid, and edges with three equivalent O(2)Rb2Pb3 trigonal bipyramids. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Pb(1), one Pb(3), and one Pb(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Pb(2), one Pb(3), and one Pb(4) atom. In the seventh O site, O(7) is bonded to one Rb(1), one Rb(2), one Pb(3), and one Pb(4) atom to form distorted ORb2Pb2 tetrahedra that share  a cornercorner with one O(3)Rb3Pb2 square pyramid, corners with three equivalent O(4)Rb3Pb2 square pyramids, corners with two equivalent O(2)Rb2Pb3 trigonal bipyramids,  an edgeedge with one O(3)Rb3Pb2 square pyramid, and  an edgeedge with one O(1)Rb2Pb3 trigonal bipyramid.