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NpGa2 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Np is bonded in a 12-coordinate geometry to two equivalent Np and twelve equivalent Ga atoms. Both Np–Np bond lengths are 2.88 Å. All Np–Ga bond lengths are 3.11 Å. Ga is bonded in a distorted q6 geometry to six equivalent Np and five equivalent Ga atoms. There are three shorter (2.76 Å) and two longer (2.88 Å) Ga–Ga bond lengths.
NpGa3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Np is bonded to twelve equivalent Ga atoms to form NpGa12 cuboctahedra that share corners with twelve equivalent NpGa12 cuboctahedra, edges with twenty-four equivalent GaNp4Ga8 cuboctahedra, faces with six equivalent NpGa12 cuboctahedra, and faces with twelve equivalent GaNp4Ga8 cuboctahedra. All Np–Ga bond lengths are 3.02 Å. Ga is bonded to four equivalent Np and eight equivalent Ga atoms to form distorted GaNp4Ga8 cuboctahedra that share corners with twelve equivalent GaNp4Ga8 cuboctahedra, edges with eight equivalent NpGa12 cuboctahedra, edges with sixteen equivalent GaNp4Ga8 cuboctahedra, faces with four equivalent NpGa12 cuboctahedra, and faces with fourteen equivalent GaNp4Ga8 cuboctahedra. All Ga–Ga bond lengths are 3.02 Å.
NpGa4 crystallizes in the orthorhombic Imma space group. The structure is three-dimensional. Np is bonded in a 9-coordinate geometry to thirteen Ga atoms. There are a spread of Np–Ga bond distances ranging from 3.03–3.14 Å. There are three inequivalent Ga sites. In the first Ga site, Ga is bonded in a 10-coordinate geometry to three equivalent Np and seven Ga atoms. There are a spread of Ga–Ga bond distances ranging from 2.61–3.05 Å. In the second Ga site, Ga is bonded in a 12-coordinate geometry to four equivalent Np and eight Ga atoms. There are four shorter (3.06 Å) and two longer (3.14 Å) Ga–Ga bond lengths. In the third Ga site, Ga is bonded in a 3-coordinate geometry to three equivalent Np and ten Ga atoms.