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NpN2 is Hydrophilite structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Np6+ is bonded to six equivalent N3- atoms to form a mixture of corner and edge-sharing NpN6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are four shorter (2.15 Å) and two longer (2.21 Å) Np–N bond lengths. N3- is bonded in a trigonal planar geometry to three equivalent Np6+ atoms.
NpN2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Np6+ is bonded in a body-centered cubic geometry to eight equivalent N3- atoms. All Np–N bond lengths are 2.26 Å. N3- is bonded to four equivalent Np6+ atoms to form a mixture of edge and corner-sharing NNp4 tetrahedra.