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NaRhCd2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two NaRhCd2 ribbons oriented in the (1, 0, 0) direction. Na is bonded in a linear geometry to two equivalent Cd atoms. Both Na–Cd bond lengths are 3.04 Å. Rh is bonded in a linear geometry to two equivalent Cd atoms. Both Rh–Cd bond lengths are 2.63 Å. Cd is bonded in a linear geometry to one Na and one Rh atom.
NaRhCd2 is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Na is bonded in a distorted body-centered cubic geometry to six equivalent Rh and eight equivalent Cd atoms. All Na–Rh bond lengths are 3.37 Å. All Na–Cd bond lengths are 2.92 Å. Rh is bonded in a distorted body-centered cubic geometry to six equivalent Na and eight equivalent Cd atoms. All Rh–Cd bond lengths are 2.92 Å. Cd is bonded in a body-centered cubic geometry to four equivalent Na and four equivalent Rh atoms.