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BaRh2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Ba is bonded in a 12-coordinate geometry to twelve equivalent Rh atoms. All Ba–Rh bond lengths are 3.30 Å. Rh is bonded to six equivalent Ba and six equivalent Rh atoms to form a mixture of edge, corner, and face-sharing RhBa6Rh6 cuboctahedra. All Rh–Rh bond lengths are 2.82 Å.
Ba4Rh is Iron carbide-like structured and crystallizes in the cubic Fd-3m space group. The structure is zero-dimensional and consists of eight Ba4Rh clusters. Ba is bonded in a single-bond geometry to one Rh atom. The Ba–Rh bond length is 2.88 Å. Rh is bonded in a tetrahedral geometry to four equivalent Ba atoms.