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RhI2 is Rutile structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Rh is bonded to six equivalent I atoms to form a mixture of edge and corner-sharing RhI6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are four shorter (2.74 Å) and two longer (2.76 Å) Rh–I bond lengths. I is bonded in a distorted trigonal planar geometry to three equivalent Rh atoms.
RhI is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. Rh is bonded to four equivalent I atoms to form corner-sharing RhI4 tetrahedra. There are three shorter (2.60 Å) and one longer (2.64 Å) Rh–I bond lengths. I is bonded to four equivalent Rh atoms to form corner-sharing IRh4 tetrahedra.
RhI3 is Aluminum trichloride structured and crystallizes in the monoclinic C2/m space group. The structure is two-dimensional and consists of one RhI3 sheet oriented in the (0, 0, 1) direction. Rh3+ is bonded to six I1- atoms to form edge-sharing RhI6 octahedra. All Rh–I bond lengths are 2.70 Å. There are two inequivalent I1- sites. In the first I1- site, I1- is bonded in an L-shaped geometry to two equivalent Rh3+ atoms. In the second I1- site, I1- is bonded in an L-shaped geometry to two equivalent Rh3+ atoms.