Hf3N2O3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form distorted HfN2O4 octahedra that share corners with two equivalent Hf(1)N2O4 octahedra, corners with two equivalent Hf(2)N3O3 octahedra, and edges with six equivalent Hf(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 25-35°. In the second Hf site, Hf(2) is bonded to three equivalent N(1), one O(1), and two equivalent O(2) atoms to form distorted HfN3O3 octahedra that share  a cornercorner with one Hf(1)N2O4 octahedra, corners with three equivalent Hf(2)N3O3 octahedra, edges with three equivalent Hf(1)N2O4 octahedra, and edges with three equivalent Hf(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 25-57°. N(1) is bonded to one Hf(1) and three equivalent Hf(2) atoms to form a mixture of corner and edge-sharing NHf4 trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to two equivalent Hf(1) and two equivalent Hf(2) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Hf(1) and two equivalent Hf(2) atoms.
Hf3N2O3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form distorted HfN2O4 octahedra that share corners with two equivalent Hf(1)N2O4 octahedra, corners with two equivalent Hf(2)N3O3 octahedra, and edges with six equivalent Hf(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 25-35°. Both Hf(1)-N(1) bond lengths are 2.13 Å. Both Hf(1)-O(1) bond lengths are 2.10 Å. Both Hf(1)-O(2) bond lengths are 2.09 Å. In the second Hf site, Hf(2) is bonded to three equivalent N(1), one O(1), and two equivalent O(2) atoms to form distorted HfN3O3 octahedra that share  a cornercorner with one Hf(1)N2O4 octahedra, corners with three equivalent Hf(2)N3O3 octahedra, edges with three equivalent Hf(1)N2O4 octahedra, and edges with three equivalent Hf(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 25-57°. There are two shorter (2.10 Å) and one longer (2.18 Å) Hf(2)-N(1) bond length. The Hf(2)-O(1) bond length is 2.30 Å. There is one shorter (2.05 Å) and one longer (2.10 Å) Hf(2)-O(2) bond length. N(1) is bonded to one Hf(1) and three equivalent Hf(2) atoms to form a mixture of corner and edge-sharing NHf4 trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to two equivalent Hf(1) and two equivalent Hf(2) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Hf(1) and two equivalent Hf(2) atoms.