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Hf2RhNi crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Hf2RhNi ribbons oriented in the (1, 0, 0) direction. Hf is bonded in a linear geometry to one Rh and one Ni atom. The Hf–Rh bond length is 2.33 Å. The Hf–Ni bond length is 2.34 Å. Rh is bonded in a linear geometry to two equivalent Hf atoms. Ni is bonded in a linear geometry to two equivalent Hf atoms.
Hf4RhNi crystallizes in the cubic F-43m space group. The structure is three-dimensional. there are three inequivalent Hf sites. In the first Hf site, Hf is bonded in a 6-coordinate geometry to three equivalent Rh and three equivalent Ni atoms. All Hf–Rh bond lengths are 2.91 Å. All Hf–Ni bond lengths are 2.61 Å. In the second Hf site, Hf is bonded in a 2-coordinate geometry to two equivalent Rh atoms. Both Hf–Rh bond lengths are 2.86 Å. In the third Hf site, Hf is bonded in a 2-coordinate geometry to two equivalent Rh and two equivalent Ni atoms. Both Hf–Rh bond lengths are 3.04 Å. Both Hf–Ni bond lengths are 2.57 Å. Rh is bonded in a 12-coordinate geometry to nine Hf atoms. Ni is bonded in a 6-coordinate geometry to six Hf atoms.