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HfRh2Zn crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two HfRh2Zn ribbons oriented in the (1, 0, 0) direction. Hf is bonded in a linear geometry to two equivalent Rh atoms. Both Hf–Rh bond lengths are 2.22 Å. Rh is bonded in a linear geometry to one Hf and one Zn atom. The Rh–Zn bond length is 2.53 Å. Zn is bonded in a linear geometry to two equivalent Rh atoms.
HfRh2Zn is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Hf is bonded in a body-centered cubic geometry to eight equivalent Rh atoms. All Hf–Rh bond lengths are 2.72 Å. Rh is bonded in a body-centered cubic geometry to four equivalent Hf and four equivalent Zn atoms. All Rh–Zn bond lengths are 2.72 Å. Zn is bonded in a body-centered cubic geometry to eight equivalent Rh atoms.