NdSi2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Nd is bonded in a 12-coordinate geometry to twelve equivalent Si atoms. All Nd–Si bond lengths are 3.20 Å. Si is bonded to six equivalent Nd and six equivalent Si atoms to form a mixture of edge, face, and corner-sharing SiNd6Si6 cuboctahedra. All Si–Si bond lengths are 2.73 Å.