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LiMg2In crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiMg2In 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 2.92 Å. Mg is bonded in a linear geometry to one Li and one In atom. The Mg–In bond length is 2.94 Å. In is bonded in a linear geometry to two equivalent Mg atoms.
LiMg2In 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 Mg atoms. All Li–Mg bond lengths are 3.00 Å. Mg is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent In atoms. All Mg–In bond lengths are 3.00 Å. In is bonded in a body-centered cubic geometry to eight equivalent Mg atoms.