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BaGa2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Ba is bonded to twelve equivalent Ga atoms to form a mixture of edge and face-sharing BaGa12 cuboctahedra. All Ba–Ga bond lengths are 3.64 Å. Ga is bonded in a 9-coordinate geometry to six equivalent Ba and three equivalent Ga atoms. All Ga–Ga bond lengths are 2.59 Å.
BaGa4 crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Ba is bonded in a 8-coordinate geometry to sixteen Ga atoms. There are eight shorter (3.52 Å) and eight longer (3.57 Å) Ba–Ga bond lengths. There are two inequivalent Ga sites. In the first Ga site, Ga is bonded in a 9-coordinate geometry to four equivalent Ba and five Ga atoms. There are one shorter (2.64 Å) and four longer (2.70 Å) Ga–Ga bond lengths. In the second Ga site, Ga is bonded in a 8-coordinate geometry to four equivalent Ba and four equivalent Ga atoms.