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NaAu2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Na is bonded in a 12-coordinate geometry to twelve equivalent Au atoms. All Na–Au bond lengths are 3.30 Å. Au is bonded to six equivalent Na and six equivalent Au atoms to form a mixture of corner, edge, and face-sharing AuNa6Au6 cuboctahedra. All Au–Au bond lengths are 2.82 Å.
Na2Au is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Na is bonded in a 4-coordinate geometry to four equivalent Au atoms. All Na–Au bond lengths are 3.10 Å. Au is bonded in a 10-coordinate geometry to eight equivalent Na and two equivalent Au atoms. Both Au–Au bond lengths are 2.81 Å.
Na3Au is alpha bismuth trifluoride structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded to four equivalent Na and four equivalent Au atoms to form distorted NaNa4Au4 tetrahedra that share corners with eight equivalent NaNa8Au4 cuboctahedra, corners with eight equivalent NaNa4Au4 tetrahedra, edges with four equivalent NaNa8Au4 cuboctahedra, edges with twelve equivalent NaNa4Au4 tetrahedra, and faces with six equivalent NaNa4Au4 tetrahedra. All Na–Na bond lengths are 3.19 Å. All Na–Au bond lengths are 3.19 Å. In the second Na site, Na is bonded to eight equivalent Na and four equivalent Au atoms to form NaNa8Au4 cuboctahedra that share corners with four equivalent NaNa8Au4 cuboctahedra, corners with sixteen equivalent NaNa4Au4 tetrahedra, edges with eight equivalent NaNa8Au4 cuboctahedra, edges with eight equivalent NaNa4Au4 tetrahedra, and faces with four equivalent NaNa8Au4 cuboctahedra. All Na–Au bond lengths are 3.61 Å. Au is bonded in a distorted body-centered cubic geometry to twelve Na atoms.