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Na3Fe is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Na is bonded in a distorted square co-planar geometry to four equivalent Fe atoms. All Na–Fe bond lengths are 3.39 Å. Fe is bonded to twelve equivalent Na atoms to form a mixture of corner and face-sharing FeNa12 cuboctahedra.
Na3Fe crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Na is bonded in a distorted see-saw-like geometry to four equivalent Fe atoms. There are two shorter (3.30 Å) and two longer (3.47 Å) Na–Fe bond lengths. Fe is bonded to twelve equivalent Na atoms to form a mixture of face and corner-sharing FeNa12 cuboctahedra.