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NaPb3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Na is bonded to twelve equivalent Pb atoms to form a mixture of face and corner-sharing NaPb12 cuboctahedra. All Na–Pb bond lengths are 3.50 Å. Pb is bonded in a square co-planar geometry to four equivalent Na atoms.
Na15Pb4 crystallizes in the cubic I-43d space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded to eight equivalent Na and four equivalent Pb atoms to form distorted NaNa8Pb4 cuboctahedra that share corners with eight equivalent PbNa12 cuboctahedra, edges with eight equivalent NaNa8Pb4 cuboctahedra, and faces with four equivalent PbNa12 cuboctahedra. There are four shorter (3.43 Å) and four longer (3.50 Å) Na–Na bond lengths. All Na–Pb bond lengths are 3.60 Å. In the second Na site, Na is bonded in a 3-coordinate geometry to two equivalent Na and three equivalent Pb atoms. There are a spread of Na–Pb bond distances ranging from 3.28–3.56 Å. Pb is bonded to twelve Na atoms to form distorted PbNa12 cuboctahedra that share corners with six equivalent NaNa8Pb4 cuboctahedra, edges with six equivalent PbNa12 cuboctahedra, faces with three equivalent NaNa8Pb4 cuboctahedra, and faces with five equivalent PbNa12 cuboctahedra.