Rb3O5I crystallizes in the orthorhombic Pnna space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form RbO5 square pyramids that share corners with five equivalent I(1)O5 trigonal bipyramids. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to two equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms. In the third Rb site, Rb(3) is bonded in a 10-coordinate geometry to two equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), two equivalent Rb(2), two equivalent Rb(3), and one I(1) atom to form distorted edge-sharing ORb5I octahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Rb(1), two equivalent Rb(2), two equivalent Rb(3), and one I(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Rb(1), two equivalent Rb(2), two equivalent Rb(3), and one I(1) atom. I(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form IO5 trigonal bipyramids that share corners with five equivalent Rb(1)O5 square pyramids.
Rb3O5I crystallizes in the orthorhombic Pnna space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form RbO5 square pyramids that share corners with five equivalent I(1)O5 trigonal bipyramids. The Rb(1)-O(1) bond length is 2.72 Å. Both Rb(1)-O(2) bond lengths are 2.81 Å. Both Rb(1)-O(3) bond lengths are 2.86 Å. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to two equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms. Both Rb(2)-O(1) bond lengths are 3.12 Å. There are two shorter (3.38 Å) and two longer (3.48 Å) Rb(2)-O(2) bond lengths. There are two shorter (2.96 Å) and two longer (3.13 Å) Rb(2)-O(3) bond lengths. In the third Rb site, Rb(3) is bonded in a 10-coordinate geometry to two equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms. Both Rb(3)-O(1) bond lengths are 3.15 Å. There are two shorter (2.96 Å) and two longer (3.20 Å) Rb(3)-O(2) bond lengths. There are two shorter (3.31 Å) and two longer (3.47 Å) Rb(3)-O(3) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Rb(1), two equivalent Rb(2), two equivalent Rb(3), and one I(1) atom to form distorted edge-sharing ORb5I octahedra. The O(1)-I(1) bond length is 1.83 Å. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Rb(1), two equivalent Rb(2), two equivalent Rb(3), and one I(1) atom. The O(2)-I(1) bond length is 1.88 Å. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Rb(1), two equivalent Rb(2), two equivalent Rb(3), and one I(1) atom. The O(3)-I(1) bond length is 1.88 Å. I(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form IO5 trigonal bipyramids that share corners with five equivalent Rb(1)O5 square pyramids.