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NaBi is Tetraauricupride structured and crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Na is bonded to eight equivalent Bi atoms to form a mixture of distorted face, edge, and corner-sharing NaBi8 cuboctahedra. All Na–Bi bond lengths are 3.46 Å. Bi is bonded to eight equivalent Na atoms to form a mixture of distorted face, edge, and corner-sharing BiNa8 cuboctahedra.
Na3Bi is Sodium arsenide structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Na sites. In the first Na site, Na is bonded in a 1-coordinate geometry to four equivalent Bi atoms. There are one shorter (3.25 Å) and three longer (3.56 Å) Na–Bi bond lengths. In the second Na site, Na is bonded in a trigonal planar geometry to three equivalent Bi atoms. All Na–Bi bond lengths are 3.17 Å. Bi is bonded in a 5-coordinate geometry to eleven Na atoms.
NaBi3 is Uranium Silicide-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Na is bonded to twelve equivalent Bi atoms to form a mixture of corner and face-sharing NaBi12 cuboctahedra. There are six shorter (3.51 Å) and six longer (3.52 Å) Na–Bi bond lengths. Bi is bonded in a distorted see-saw-like geometry to four equivalent Na atoms.
Na3Bi is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m 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 Bi atoms to form a mixture of distorted edge, face, and corner-sharing NaNa4Bi4 tetrahedra. All Na–Na bond lengths are 3.34 Å. All Na–Bi bond lengths are 3.34 Å. In the second Na site, Na is bonded in a 8-coordinate geometry to eight equivalent Na and six equivalent Bi atoms. All Na–Bi bond lengths are 3.85 Å. Bi is bonded in a body-centered cubic geometry to fourteen Na atoms.