Rb2Bi(O3I)5 crystallizes in the orthorhombic Aem2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent O(4), two equivalent O(5), and four equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded to two equivalent O(6), two equivalent O(8), and four equivalent O(2) atoms to form distorted edge-sharing RbO8 hexagonal bipyramids. Bi(1) is bonded in a 8-coordinate geometry to two equivalent O(4), two equivalent O(5), and four equivalent O(3) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Rb(1) and one I(2) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to two equivalent Rb(2) and one I(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Bi(1) and one I(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Rb(1), one Bi(1), and one I(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Rb(1), one Bi(1), and one I(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Rb(2) and one I(1) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one I(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Rb(2), one I(2), and one I(3) atom. There are three inequivalent I sites. In the first I site, I(1) is bonded in a distorted trigonal non-coplanar geometry to one O(2), one O(5), and one O(6) atom. In the second I site, I(2) is bonded in a 3-coordinate geometry to one O(1), one O(3), one O(4), and one O(8) atom. In the third I site, I(3) is bonded in a 3-coordinate geometry to one O(7) and two equivalent O(8) atoms.
Rb2Bi(O3I)5 crystallizes in the orthorhombic Aem2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent O(4), two equivalent O(5), and four equivalent O(1) atoms. Both Rb(1)-O(4) bond lengths are 3.29 Å. Both Rb(1)-O(5) bond lengths are 3.13 Å. There are two shorter (2.88 Å) and two longer (2.98 Å) Rb(1)-O(1) bond lengths. In the second Rb site, Rb(2) is bonded to two equivalent O(6), two equivalent O(8), and four equivalent O(2) atoms to form distorted edge-sharing RbO8 hexagonal bipyramids. Both Rb(2)-O(6) bond lengths are 3.18 Å. Both Rb(2)-O(8) bond lengths are 3.24 Å. There are two shorter (2.98 Å) and two longer (3.08 Å) Rb(2)-O(2) bond lengths. Bi(1) is bonded in a 8-coordinate geometry to two equivalent O(4), two equivalent O(5), and four equivalent O(3) atoms. Both Bi(1)-O(4) bond lengths are 2.54 Å. Both Bi(1)-O(5) bond lengths are 2.38 Å. There are two shorter (2.37 Å) and two longer (2.76 Å) Bi(1)-O(3) bond lengths. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Rb(1) and one I(2) atom. The O(1)-I(2) bond length is 1.81 Å. In the second O site, O(2) is bonded in a 1-coordinate geometry to two equivalent Rb(2) and one I(1) atom. The O(2)-I(1) bond length is 1.83 Å. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Bi(1) and one I(2) atom. The O(3)-I(2) bond length is 1.90 Å. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Rb(1), one Bi(1), and one I(2) atom. The O(4)-I(2) bond length is 1.85 Å. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Rb(1), one Bi(1), and one I(1) atom. The O(5)-I(1) bond length is 1.85 Å. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Rb(2) and one I(1) atom. The O(6)-I(1) bond length is 1.83 Å. In the seventh O site, O(7) is bonded in a single-bond geometry to one I(3) atom. The O(7)-I(3) bond length is 1.84 Å. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Rb(2), one I(2), and one I(3) atom. The O(8)-I(2) bond length is 2.49 Å. The O(8)-I(3) bond length is 1.84 Å. There are three inequivalent I sites. In the first I site, I(1) is bonded in a distorted trigonal non-coplanar geometry to one O(2), one O(5), and one O(6) atom. In the second I site, I(2) is bonded in a 3-coordinate geometry to one O(1), one O(3), one O(4), and one O(8) atom. In the third I site, I(3) is bonded in a 3-coordinate geometry to one O(7) and two equivalent O(8) atoms.