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CaRh2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Ca is bonded in a 12-coordinate geometry to twelve equivalent Rh atoms. All Ca–Rh bond lengths are 3.14 Å. Rh is bonded to six equivalent Ca and six equivalent Rh atoms to form a mixture of corner, edge, and face-sharing RhCa6Rh6 cuboctahedra. All Rh–Rh bond lengths are 2.68 Å.
Ca2Rh is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ca is bonded to four equivalent Rh atoms to form a mixture of corner and edge-sharing CaRh4 tetrahedra. All Ca–Rh bond lengths are 3.01 Å. Rh is bonded in a body-centered cubic geometry to eight equivalent Ca atoms.
Ca4Rh is Iron carbide-like structured and crystallizes in the cubic Fd-3m space group. The structure is zero-dimensional and consists of eight Ca4Rh clusters. Ca is bonded in a single-bond geometry to one Rh atom. The Ca–Rh bond length is 2.58 Å. Rh is bonded in a tetrahedral geometry to four equivalent Ca atoms.