RbI(OF)2 crystallizes in the orthorhombic Pca2_1 space group. Rb(1) is bonded in a 9-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent F(1), and three equivalent F(2) atoms. There are two 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(1) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to two equivalent Rb(1) and one I(1) atom. I(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one F(1), and one F(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Rb(1) and one I(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to three equivalent Rb(1) and one I(1) atom.
RbI(OF)2 crystallizes in the orthorhombic Pca2_1 space group. Rb(1) is bonded in a 9-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent F(1), and three equivalent F(2) atoms. There is one shorter (3.05 Å) and one longer (3.09 Å) Rb(1)-O(1) bond length. There is one shorter (2.96 Å) and one longer (3.50 Å) Rb(1)-O(2) bond length. There is one shorter (2.94 Å) and one longer (3.18 Å) Rb(1)-F(1) bond length. There are a spread of Rb(1)-F(2) bond distances ranging from 2.86-3.15 Å. There are two 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(1) atom. The O(1)-I(1) bond length is 1.81 Å. In the second O site, O(2) is bonded in a 1-coordinate geometry to two equivalent Rb(1) and one I(1) atom. The O(2)-I(1) bond length is 1.80 Å. I(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one F(1), and one F(2) atom. The I(1)-F(1) bond length is 2.04 Å. The I(1)-F(2) bond length is 2.07 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to two equivalent Rb(1) and one I(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to three equivalent Rb(1) and one I(1) atom.