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LiMg2Au crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiMg2Au ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Mg atoms. Both Li–Mg bond lengths are 2.88 Å. Mg is bonded in a linear geometry to one Li and one Au atom. The Mg–Au bond length is 2.65 Å. Au is bonded in a linear geometry to two equivalent Mg atoms.
LiMg2Au is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Li is bonded in a distorted body-centered cubic geometry to eight equivalent Mg and six equivalent Au atoms. All Li–Mg bond lengths are 2.85 Å. All Li–Au bond lengths are 3.29 Å. Mg is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Au atoms. All Mg–Au bond lengths are 2.85 Å. Au is bonded in a body-centered cubic geometry to six equivalent Li and eight equivalent Mg atoms.