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Li2MgAu crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Li2MgAu ribbons oriented in the (0, 1, 0) direction. Li is bonded in a linear geometry to one Mg and one Au atom. The Li–Mg bond length is 3.03 Å. The Li–Au bond length is 2.47 Å. Mg is bonded in a linear geometry to two equivalent Li atoms. Au is bonded in a linear geometry to two equivalent Li atoms.
Li2MgAu crystallizes in the cubic F-43m space group. The structure is three-dimensional. there are two inequivalent Li sites. In the first Li site, Li is bonded in a 4-coordinate geometry to four equivalent Li, four equivalent Mg, and six equivalent Au atoms. All Li–Li bond lengths are 2.80 Å. All Li–Mg bond lengths are 2.80 Å. All Li–Au bond lengths are 3.24 Å. In the second Li site, Li is bonded to four equivalent Li and four equivalent Au atoms to form distorted edge-sharing LiLi4Au4 tetrahedra. All Li–Au bond lengths are 2.80 Å. Mg is bonded in a distorted body-centered cubic geometry to four equivalent Li and four equivalent Au atoms. All Mg–Au bond lengths are 2.80 Å. Au is bonded in a distorted body-centered cubic geometry to ten Li and four equivalent Mg atoms.