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NiN is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. Ni3+ is bonded to four equivalent N3- atoms to form corner-sharing NiN4 tetrahedra. There is three shorter (1.87 Å) and one longer (1.88 Å) Ni–N bond length. N3- is bonded to four equivalent Ni3+ atoms to form corner-sharing NNi4 tetrahedra.
NiN crystallizes in the tetragonal P4_2/mmc space group. The structure is one-dimensional and consists of two NiN ribbons oriented in the (1, 0, 0) direction. Ni3+ is bonded in a linear geometry to two equivalent N3- atoms. Both Ni–N bond lengths are 1.68 Å. N3- is bonded in a linear geometry to two equivalent Ni3+ atoms.