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CuGa2 crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Cu is bonded in a distorted body-centered cubic geometry to eight equivalent Ga atoms. All Cu–Ga bond lengths are 2.62 Å. Ga is bonded in a 9-coordinate geometry to four equivalent Cu and five equivalent Ga atoms. There are one shorter (2.54 Å) and four longer (2.84 Å) Ga–Ga bond lengths.
CuGa3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Cu is bonded to twelve equivalent Ga atoms to form CuGa12 cuboctahedra that share corners with twelve equivalent CuGa12 cuboctahedra, edges with twenty-four equivalent GaGa8Cu4 cuboctahedra, faces with six equivalent CuGa12 cuboctahedra, and faces with twelve equivalent GaGa8Cu4 cuboctahedra. All Cu–Ga bond lengths are 2.85 Å. Ga is bonded to four equivalent Cu and eight equivalent Ga atoms to form GaGa8Cu4 cuboctahedra that share corners with twelve equivalent GaGa8Cu4 cuboctahedra, edges with eight equivalent CuGa12 cuboctahedra, edges with sixteen equivalent GaGa8Cu4 cuboctahedra, faces with four equivalent CuGa12 cuboctahedra, and faces with fourteen equivalent GaGa8Cu4 cuboctahedra. All Ga–Ga bond lengths are 2.85 Å.
Cu3Ga is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Cu sites. In the first Cu site, Cu is bonded to eight Cu and four equivalent Ga atoms to form CuGa4Cu8 cuboctahedra that share corners with four equivalent GaCu12 cuboctahedra, corners with fourteen equivalent CuGa4Cu8 cuboctahedra, edges with six equivalent GaCu12 cuboctahedra, edges with twelve CuGa4Cu8 cuboctahedra, faces with four equivalent GaCu12 cuboctahedra, and faces with sixteen CuGa4Cu8 cuboctahedra. There are six shorter (2.59 Å) and two longer (2.63 Å) Cu–Cu bond lengths. There are two shorter (2.60 Å) and two longer (2.61 Å) Cu–Ga bond lengths. In the second Cu site, Cu is bonded to eight equivalent Cu and four equivalent Ga atoms to form CuGa4Cu8 cuboctahedra that share corners with four equivalent GaCu12 cuboctahedra, corners with fourteen CuGa4Cu8 cuboctahedra, edges with six equivalent GaCu12 cuboctahedra, edges with twelve equivalent CuGa4Cu8 cuboctahedra, faces with four equivalent GaCu12 cuboctahedra, and faces with sixteen CuGa4Cu8 cuboctahedra. There are two shorter (2.60 Å) and two longer (2.61 Å) Cu–Ga bond lengths. Ga is bonded to twelve Cu atoms to form GaCu12 cuboctahedra that share corners with six equivalent GaCu12 cuboctahedra, corners with twelve CuGa4Cu8 cuboctahedra, edges with eighteen CuGa4Cu8 cuboctahedra, faces with eight equivalent GaCu12 cuboctahedra, and faces with twelve CuGa4Cu8 cuboctahedra.
Cu2Ga crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Cu is bonded in a 11-coordinate geometry to five equivalent Cu and six equivalent Ga atoms. There are a spread of Cu–Cu bond distances ranging from 2.42–2.62 Å. There are a spread of Cu–Ga bond distances ranging from 2.73–2.79 Å. Ga is bonded in a 12-coordinate geometry to twelve equivalent Cu and two equivalent Ga atoms. Both Ga–Ga bond lengths are 2.59 Å.
Cu4Ga is alpha La-derived structured and crystallizes in the trigonal R-3m space group. The structure is three-dimensional. there are five inequivalent Cu sites. In the first Cu site, Cu is bonded to nine Cu and three equivalent Ga atoms to form CuGa3Cu9 cuboctahedra that share corners with twelve CuGa3Cu9 cuboctahedra, edges with six equivalent GaGa6Cu6 cuboctahedra, edges with eighteen CuGa3Cu9 cuboctahedra, faces with six equivalent GaGa6Cu6 cuboctahedra, and faces with twelve CuGa3Cu9 cuboctahedra. There are three shorter (2.56 Å) and six longer (2.65 Å) Cu–Cu bond lengths. All Cu–Ga bond lengths are 2.62 Å. In the second Cu site, Cu is bonded to twelve Cu atoms to form CuCu12 cuboctahedra that share corners with three equivalent GaGa6Cu6 cuboctahedra, corners with nine CuGa3Cu9 cuboctahedra, edges with three equivalent GaGa6Cu6 cuboctahedra, edges with twenty-one CuGa3Cu9 cuboctahedra, and faces with eighteen CuGa3Cu9 cuboctahedra. There are three shorter (2.56 Å) and six longer (2.65 Å) Cu–Cu bond lengths. In the third Cu site, Cu is bonded to twelve Cu atoms to form CuCu12 cuboctahedra that share corners with three equivalent GaGa6Cu6 cuboctahedra, corners with nine CuGa3Cu9 cuboctahedra, edges with three equivalent GaGa6Cu6 cuboctahedra, edges with twenty-one CuGa3Cu9 cuboctahedra, and faces with eighteen CuGa3Cu9 cuboctahedra. There are three shorter (2.56 Å) and six longer (2.65 Å) Cu–Cu bond lengths. In the fourth Cu site, Cu is bonded to twelve Cu atoms to form CuCu12 cuboctahedra that share corners with three equivalent GaGa6Cu6 cuboctahedra, corners with nine CuCu12 cuboctahedra, edges with three equivalent GaGa6Cu6 cuboctahedra, edges with twenty-one CuCu12 cuboctahedra, and faces with eighteen CuCu12 cuboctahedra. There are six shorter (2.56 Å) and six longer (2.65 Å) Cu–Cu bond lengths. In the fifth Cu site, Cu is bonded to twelve Cu atoms to form CuCu12 cuboctahedra that share corners with three equivalent GaGa6Cu6 cuboctahedra, corners with nine CuGa3Cu9 cuboctahedra, edges with three equivalent GaGa6Cu6 cuboctahedra, edges with twenty-one CuGa3Cu9 cuboctahedra, and faces with eighteen CuGa3Cu9 cuboctahedra. There are six shorter (2.56 Å) and six longer (2.65 Å) Cu–Cu bond lengths. Ga is bonded to six equivalent Cu and six equivalent Ga atoms to form GaGa6Cu6 cuboctahedra that share corners with six CuCu12 cuboctahedra, corners with six equivalent GaGa6Cu6 cuboctahedra, edges with six equivalent GaGa6Cu6 cuboctahedra, edges with eighteen CuGa3Cu9 cuboctahedra, faces with six equivalent GaGa6Cu6 cuboctahedra, and faces with twelve equivalent CuGa3Cu9 cuboctahedra. All Ga–Ga bond lengths are 2.65 Å.