Li3NdGa8 crystallizes in the hexagonal P6/mmm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Ga(1) and six equivalent Ga(2) atoms to form LiGa12 cuboctahedra that share edges with six equivalent Li(2)Ga12 cuboctahedra, edges with six equivalent Nd(1)Ga12 cuboctahedra,  a faceface with one Li(2)Ga12 cuboctahedra,  a faceface with one Nd(1)Ga12 cuboctahedra, and faces with six equivalent Li(1)Ga12 cuboctahedra. In the second Li site, Li(2) is bonded to twelve equivalent Ga(2) atoms to form a mixture of face and edge-sharing LiGa12 cuboctahedra. Nd(1) is bonded to twelve equivalent Ga(1) atoms to form distorted NdGa12 cuboctahedra that share edges with twelve equivalent Li(1)Ga12 cuboctahedra, faces with two equivalent Li(1)Ga12 cuboctahedra, and faces with six equivalent Nd(1)Ga12 cuboctahedra. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 9-coordinate geometry to three equivalent Li(1), three equivalent Nd(1), and three equivalent Ga(1) atoms. In the second Ga site, Ga(2) is bonded in a 9-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and three equivalent Ga(2) atoms.
Li3NdGa8 crystallizes in the hexagonal P6/mmm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Ga(1) and six equivalent Ga(2) atoms to form LiGa12 cuboctahedra that share edges with six equivalent Li(2)Ga12 cuboctahedra, edges with six equivalent Nd(1)Ga12 cuboctahedra,  a faceface with one Li(2)Ga12 cuboctahedra,  a faceface with one Nd(1)Ga12 cuboctahedra, and faces with six equivalent Li(1)Ga12 cuboctahedra. All Li(1)-Ga(1) bond lengths are 2.93 Å. All Li(1)-Ga(2) bond lengths are 2.97 Å. In the second Li site, Li(2) is bonded to twelve equivalent Ga(2) atoms to form a mixture of face and edge-sharing LiGa12 cuboctahedra. All Li(2)-Ga(2) bond lengths are 3.07 Å. Nd(1) is bonded to twelve equivalent Ga(1) atoms to form distorted NdGa12 cuboctahedra that share edges with twelve equivalent Li(1)Ga12 cuboctahedra, faces with two equivalent Li(1)Ga12 cuboctahedra, and faces with six equivalent Nd(1)Ga12 cuboctahedra. All Nd(1)-Ga(1) bond lengths are 3.21 Å. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a 9-coordinate geometry to three equivalent Li(1), three equivalent Nd(1), and three equivalent Ga(1) atoms. All Ga(1)-Ga(1) bond lengths are 2.51 Å. In the second Ga site, Ga(2) is bonded in a 9-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and three equivalent Ga(2) atoms. All Ga(2)-Ga(2) bond lengths are 2.51 Å.