Rb2PbO2 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(3) atoms. In the third Rb site, Rb(3) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted edge-sharing RbO5 trigonal bipyramids. In the fourth Rb site, Rb(4) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted edge-sharing RbO5 square pyramids. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 3-coordinate geometry to one O(1) and two equivalent O(2) atoms. In the second Pb site, Pb(2) is bonded in a 3-coordinate geometry to one O(3) and two equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Rb(3), two equivalent Rb(1), two equivalent Rb(4), and one Pb(1) atom to form distorted ORb5Pb octahedra that share corners with three equivalent O(3)Rb5Pb octahedra,  a cornercorner with one O(4)Rb3Pb2 trigonal bipyramid,  an edgeedge with one O(3)Rb5Pb octahedra, edges with two equivalent O(1)Rb5Pb octahedra, edges with four equivalent O(2)Rb4Pb2 octahedra, and  an edgeedge with one O(4)Rb3Pb2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 15-18°. In the second O site, O(2) is bonded to one Rb(1), one Rb(4), two equivalent Rb(3), and two equivalent Pb(1) atoms to form ORb4Pb2 octahedra that share corners with three equivalent O(4)Rb3Pb2 trigonal bipyramids, edges with two equivalent O(2)Rb4Pb2 octahedra, edges with two equivalent O(3)Rb5Pb octahedra, and edges with four equivalent O(1)Rb5Pb octahedra. In the third O site, O(3) is bonded to one Rb(1), one Rb(3), one Rb(4), two equivalent Rb(2), and one Pb(2) atom to form distorted ORb5Pb octahedra that share corners with three equivalent O(1)Rb5Pb octahedra,  an edgeedge with one O(1)Rb5Pb octahedra,  an edgeedge with one O(3)Rb5Pb octahedra, edges with two equivalent O(2)Rb4Pb2 octahedra, and edges with three equivalent O(4)Rb3Pb2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-18°. In the fourth O site, O(4) is bonded to one Rb(2), one Rb(3), one Rb(4), and two equivalent Pb(2) atoms to form distorted ORb3Pb2 trigonal bipyramids that share  a cornercorner with one O(1)Rb5Pb octahedra, corners with three equivalent O(2)Rb4Pb2 octahedra,  an edgeedge with one O(1)Rb5Pb octahedra, edges with three equivalent O(3)Rb5Pb octahedra, and  an edgeedge with one O(4)Rb3Pb2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-78°.
Rb2PbO2 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a distorted see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Rb(1)-O(2) bond length is 2.81 Å. The Rb(1)-O(3) bond length is 3.01 Å. There is one shorter (2.83 Å) and one longer (2.86 Å) Rb(1)-O(1) bond length. In the second Rb site, Rb(2) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(3) atoms. The Rb(2)-O(4) bond length is 2.80 Å. There is one shorter (2.79 Å) and one longer (2.82 Å) Rb(2)-O(3) bond length. In the third Rb site, Rb(3) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted edge-sharing RbO5 trigonal bipyramids. The Rb(3)-O(1) bond length is 2.96 Å. The Rb(3)-O(3) bond length is 2.88 Å. The Rb(3)-O(4) bond length is 2.80 Å. There is one shorter (2.98 Å) and one longer (3.00 Å) Rb(3)-O(2) bond length. In the fourth Rb site, Rb(4) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted edge-sharing RbO5 square pyramids. The Rb(4)-O(2) bond length is 2.94 Å. The Rb(4)-O(3) bond length is 2.92 Å. The Rb(4)-O(4) bond length is 2.91 Å. There is one shorter (2.84 Å) and one longer (2.86 Å) Rb(4)-O(1) bond length. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 3-coordinate geometry to one O(1) and two equivalent O(2) atoms. The Pb(1)-O(1) bond length is 2.12 Å. There is one shorter (2.23 Å) and one longer (2.27 Å) Pb(1)-O(2) bond length. In the second Pb site, Pb(2) is bonded in a 3-coordinate geometry to one O(3) and two equivalent O(4) atoms. The Pb(2)-O(3) bond length is 2.13 Å. There is one shorter (2.23 Å) and one longer (2.24 Å) Pb(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Rb(3), two equivalent Rb(1), two equivalent Rb(4), and one Pb(1) atom to form distorted ORb5Pb octahedra that share corners with three equivalent O(3)Rb5Pb octahedra,  a cornercorner with one O(4)Rb3Pb2 trigonal bipyramid,  an edgeedge with one O(3)Rb5Pb octahedra, edges with two equivalent O(1)Rb5Pb octahedra, edges with four equivalent O(2)Rb4Pb2 octahedra, and  an edgeedge with one O(4)Rb3Pb2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 15-18°. In the second O site, O(2) is bonded to one Rb(1), one Rb(4), two equivalent Rb(3), and two equivalent Pb(1) atoms to form ORb4Pb2 octahedra that share corners with three equivalent O(4)Rb3Pb2 trigonal bipyramids, edges with two equivalent O(2)Rb4Pb2 octahedra, edges with two equivalent O(3)Rb5Pb octahedra, and edges with four equivalent O(1)Rb5Pb octahedra. In the third O site, O(3) is bonded to one Rb(1), one Rb(3), one Rb(4), two equivalent Rb(2), and one Pb(2) atom to form distorted ORb5Pb octahedra that share corners with three equivalent O(1)Rb5Pb octahedra,  an edgeedge with one O(1)Rb5Pb octahedra,  an edgeedge with one O(3)Rb5Pb octahedra, edges with two equivalent O(2)Rb4Pb2 octahedra, and edges with three equivalent O(4)Rb3Pb2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 15-18°. In the fourth O site, O(4) is bonded to one Rb(2), one Rb(3), one Rb(4), and two equivalent Pb(2) atoms to form distorted ORb3Pb2 trigonal bipyramids that share  a cornercorner with one O(1)Rb5Pb octahedra, corners with three equivalent O(2)Rb4Pb2 octahedra,  an edgeedge with one O(1)Rb5Pb octahedra, edges with three equivalent O(3)Rb5Pb octahedra, and  an edgeedge with one O(4)Rb3Pb2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-78°.