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LiHfAu2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiHfAu2 ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Au atoms. Both Li–Au bond lengths are 2.67 Å. Hf is bonded in a linear geometry to two equivalent Au atoms. Both Hf–Au bond lengths are 2.64 Å. Au is bonded in a linear geometry to one Li and one Hf atom.
LiHfAu2 is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Li is bonded in a body-centered cubic geometry to eight equivalent Au atoms. All Li–Au bond lengths are 2.85 Å. Hf is bonded in a body-centered cubic geometry to eight equivalent Au atoms. All Hf–Au bond lengths are 2.85 Å. Au is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Hf atoms.