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HfN2 crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. Hf4+ is bonded in a 6-coordinate geometry to six equivalent N2- atoms. All Hf–N bond lengths are 2.23 Å. N2- is bonded in a 4-coordinate geometry to three equivalent Hf4+ and one N2- atom. The N–N bond length is 1.44 Å.
HfN2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Hf4+ is bonded in a 6-coordinate geometry to six equivalent N2- atoms. All Hf–N bond lengths are 2.22 Å. N2- is bonded in a 4-coordinate geometry to three equivalent Hf4+ and one N2- atom. The N–N bond length is 1.43 Å.
HfN2 is Pyrite-like structured and crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Hf4+ is bonded to six equivalent N2- atoms to form HfN6 octahedra that share corners with twelve equivalent HfN6 octahedra and corners with six equivalent NHf3N tetrahedra. The corner-sharing octahedral tilt angles are 70°. All Hf–N bond lengths are 2.21 Å. N2- is bonded to three equivalent Hf4+ and one N2- atom to form NHf3N tetrahedra that share corners with three equivalent HfN6 octahedra and corners with fifteen equivalent NHf3N tetrahedra. The corner-sharing octahedral tilt angles are 71°. The N–N bond length is 1.51 Å.