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LiSc2Ga crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two LiSc2Ga ribbons oriented in the (0, 1, 0) direction. Li is bonded in a linear geometry to two equivalent Sc atoms. Both Li–Sc bond lengths are 3.26 Å. Sc is bonded in a linear geometry to one Li and one Ga atom. The Sc–Ga bond length is 2.59 Å. Ga is bonded in a linear geometry to two equivalent Sc atoms.
LiSc2Ga 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 Sc atoms. All Li–Sc bond lengths are 2.93 Å. Sc is bonded in a body-centered cubic geometry to four equivalent Li and four equivalent Ga atoms. All Sc–Ga bond lengths are 2.93 Å. Ga is bonded in a body-centered cubic geometry to eight equivalent Sc atoms.