RbPbO2I3 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 9-coordinate geometry to two equivalent O(1), one I(2), two equivalent I(3), and four equivalent I(1) atoms. Pb(1) is bonded to one I(1), two equivalent I(3), and three equivalent I(2) atoms to form edge-sharing PbI6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Rb(1) and one O(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one O(1) atom. There are three inequivalent I sites. In the first I site, I(1) is bonded to four equivalent Rb(1) and one Pb(1) atom to form IRb4Pb square pyramids that share corners with four equivalent I(1)Rb4Pb square pyramids, corners with two equivalent I(3)Rb2Pb2 trigonal pyramids, edges with four equivalent I(1)Rb4Pb square pyramids, and edges with four equivalent I(3)Rb2Pb2 trigonal pyramids. In the second I site, I(2) is bonded in a rectangular see-saw-like geometry to one Rb(1) and three equivalent Pb(1) atoms. In the third I site, I(3) is bonded to two equivalent Rb(1) and two equivalent Pb(1) atoms to form IRb2Pb2 trigonal pyramids that share corners with two equivalent I(1)Rb4Pb square pyramids, corners with four equivalent I(3)Rb2Pb2 trigonal pyramids, and edges with four equivalent I(1)Rb4Pb square pyramids.
RbPbO2I3 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 9-coordinate geometry to two equivalent O(1), one I(2), two equivalent I(3), and four equivalent I(1) atoms. Both Rb(1)-O(1) bond lengths are 3.34 Å. The Rb(1)-I(2) bond length is 3.84 Å. There is one shorter (4.02 Å) and one longer (4.07 Å) Rb(1)-I(3) bond length. There are two shorter (3.69 Å) and two longer (3.79 Å) Rb(1)-I(1) bond lengths. Pb(1) is bonded to one I(1), two equivalent I(3), and three equivalent I(2) atoms to form edge-sharing PbI6 octahedra. The Pb(1)-I(1) bond length is 3.16 Å. Both Pb(1)-I(3) bond lengths are 3.23 Å. There are two shorter (3.35 Å) and one longer (3.40 Å) Pb(1)-I(2) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Rb(1) and one O(2) atom. The O(1)-O(2) bond length is 1.23 Å. In the second O site, O(2) is bonded in a single-bond geometry to one O(1) atom. There are three inequivalent I sites. In the first I site, I(1) is bonded to four equivalent Rb(1) and one Pb(1) atom to form IRb4Pb square pyramids that share corners with four equivalent I(1)Rb4Pb square pyramids, corners with two equivalent I(3)Rb2Pb2 trigonal pyramids, edges with four equivalent I(1)Rb4Pb square pyramids, and edges with four equivalent I(3)Rb2Pb2 trigonal pyramids. In the second I site, I(2) is bonded in a rectangular see-saw-like geometry to one Rb(1) and three equivalent Pb(1) atoms. In the third I site, I(3) is bonded to two equivalent Rb(1) and two equivalent Pb(1) atoms to form IRb2Pb2 trigonal pyramids that share corners with two equivalent I(1)Rb4Pb square pyramids, corners with four equivalent I(3)Rb2Pb2 trigonal pyramids, and edges with four equivalent I(1)Rb4Pb square pyramids.