Ti3N2O3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form distorted TiN2O4 octahedra that share corners with two equivalent Ti(1)N2O4 octahedra, corners with two equivalent Ti(2)N3O3 octahedra, and edges with six equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-30°. In the second Ti site, Ti(2) is bonded to three equivalent N(1), one O(1), and two equivalent O(2) atoms to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(1)N2O4 octahedra, corners with three equivalent Ti(2)N3O3 octahedra, edges with three equivalent Ti(1)N2O4 octahedra, and edges with three equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-56°. N(1) is bonded to one Ti(1) and three equivalent Ti(2) atoms to form a mixture of edge and corner-sharing NTi4 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 Ti(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms.
Ti3N2O3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form distorted TiN2O4 octahedra that share corners with two equivalent Ti(1)N2O4 octahedra, corners with two equivalent Ti(2)N3O3 octahedra, and edges with six equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-30°. Both Ti(1)-N(1) bond lengths are 2.00 Å. Both Ti(1)-O(1) bond lengths are 1.98 Å. Both Ti(1)-O(2) bond lengths are 1.99 Å. In the second Ti site, Ti(2) is bonded to three equivalent N(1), one O(1), and two equivalent O(2) atoms to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(1)N2O4 octahedra, corners with three equivalent Ti(2)N3O3 octahedra, edges with three equivalent Ti(1)N2O4 octahedra, and edges with three equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-56°. There are two shorter (1.99 Å) and one longer (2.05 Å) Ti(2)-N(1) bond length. The Ti(2)-O(1) bond length is 2.19 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Ti(2)-O(2) bond length. N(1) is bonded to one Ti(1) and three equivalent Ti(2) atoms to form a mixture of edge and corner-sharing NTi4 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 Ti(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms.