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ScGa2 crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Sc is bonded in a 10-coordinate geometry to ten equivalent Ga atoms. There are a spread of Sc–Ga bond distances ranging from 2.95–3.02 Å. Ga is bonded in a 9-coordinate geometry to five equivalent Sc and four equivalent Ga atoms. There are a spread of Ga–Ga bond distances ranging from 2.53–2.70 Å.
ScGa2 crystallizes in the orthorhombic Cmmm space group. The structure is three-dimensional. Sc is bonded in a 10-coordinate geometry to ten Ga atoms. There are a spread of Sc–Ga bond distances ranging from 2.83–3.00 Å. There are three inequivalent Ga sites. In the first Ga site, Ga is bonded in a distorted square co-planar geometry to four equivalent Sc and four equivalent Ga atoms. All Ga–Ga bond lengths are 3.06 Å. In the second Ga site, Ga is bonded in a distorted square co-planar geometry to four equivalent Sc and four equivalent Ga atoms. All Ga–Ga bond lengths are 3.05 Å. In the third Ga site, Ga is bonded to six equivalent Sc and six Ga atoms to form a mixture of distorted corner, edge, and face-sharing GaSc6Ga6 cuboctahedra. Both Ga–Ga bond lengths are 2.78 Å.