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Li2MgGa crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Li2MgGa ribbons oriented in the (0, 1, 0) direction. Li is bonded in a linear geometry to one Mg and one Ga atom. The Li–Mg bond length is 3.03 Å. The Li–Ga bond length is 2.74 Å. Mg is bonded in a linear geometry to two equivalent Li atoms. Ga is bonded in a linear geometry to two equivalent Li atoms.
Li2MgGa 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 Mg atoms. All Li–Mg bond lengths are 2.83 Å. In the second Li site, Li is bonded to four equivalent Ga atoms to form distorted corner-sharing LiGa4 tetrahedra. All Li–Ga bond lengths are 2.83 Å. Mg is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Ga atoms. All Mg–Ga bond lengths are 2.83 Å. Ga is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Mg atoms.