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MgAu2Al crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two MgAu2Al ribbons oriented in the (1, 0, 0) direction. Mg is bonded in a linear geometry to two equivalent Au atoms. Both Mg–Au bond lengths are 2.63 Å. Au is bonded in a linear geometry to one Mg and one Al atom. The Au–Al bond length is 2.44 Å. Al is bonded in a linear geometry to two equivalent Au atoms.
MgAu2Al is Heusler structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Mg is bonded in a body-centered cubic geometry to eight equivalent Au atoms. All Mg–Au bond lengths are 2.82 Å. Au is bonded in a body-centered cubic geometry to four equivalent Mg and four equivalent Al atoms. All Au–Al bond lengths are 2.82 Å. Al is bonded in a body-centered cubic geometry to eight equivalent Au atoms.