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Nd4Bi3 crystallizes in the cubic I-43d space group. The structure is three-dimensional. Nd is bonded in a 6-coordinate geometry to six equivalent Bi atoms. There are three shorter (3.24 Å) and three longer (3.48 Å) Nd–Bi bond lengths. Bi is bonded to eight equivalent Nd atoms to form a mixture of distorted corner, edge, and face-sharing BiNd8 hexagonal bipyramids.
Bi(Nd) is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Nd is bonded to six equivalent Bi atoms to form a mixture of edge and corner-sharing NdBi6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Nd–Bi bond lengths are 3.26 Å. Bi is bonded to six equivalent Nd atoms to form a mixture of edge and corner-sharing BiNd6 octahedra. The corner-sharing octahedral tilt angles are 0°.
Nd2Bi crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Nd sites. In the first Nd site, Nd is bonded in a 4-coordinate geometry to four equivalent Nd and four equivalent Bi atoms. All Nd–Nd bond lengths are 3.29 Å. All Nd–Bi bond lengths are 3.44 Å. In the second Nd site, Nd is bonded to five equivalent Bi atoms to form a mixture of distorted corner and edge-sharing NdBi5 square pyramids. There are one shorter (3.31 Å) and four longer (3.37 Å) Nd–Bi bond lengths. Bi is bonded in a 9-coordinate geometry to nine Nd atoms.