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LiY2Ga crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiY2Ga ribbons oriented in the (1, 0, 0) direction. Li is bonded in a linear geometry to two equivalent Y atoms. Both Li–Y bond lengths are 3.31 Å. Y is bonded in a linear geometry to one Li and one Ga atom. The Y–Ga bond length is 2.63 Å. Ga is bonded in a linear geometry to two equivalent Y atoms.
LiY2Ga 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 Y atoms. All Li–Y bond lengths are 3.13 Å. Y is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Ga atoms. All Y–Ga bond lengths are 3.13 Å. Ga is bonded in a body-centered cubic geometry to eight equivalent Y atoms.