Ti2N2O crystallizes in the monoclinic C2/m space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one N(1), two equivalent O(2), and three equivalent O(1) atoms to form TiNO5 octahedra that share  a cornercorner with one Ti(2)N6 octahedra, edges with two equivalent Ti(4)N5O octahedra, and edges with four equivalent Ti(1)NO5 octahedra. The corner-sharing octahedral tilt angles are 18°. In the second Ti site, Ti(2) is bonded to one N(1), one N(2), two equivalent N(3), and two equivalent N(4) atoms to form TiN6 octahedra that share  a cornercorner with one Ti(1)NO5 octahedra, corners with two equivalent Ti(4)N5O octahedra, corners with three equivalent Ti(3)N6 octahedra, edges with two equivalent Ti(2)N6 octahedra, edges with three equivalent Ti(4)N5O octahedra, and edges with three equivalent Ti(3)N6 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. In the third Ti site, Ti(3) is bonded to one N(3), two equivalent N(4), and three equivalent N(2) atoms to form TiN6 octahedra that share corners with three equivalent Ti(2)N6 octahedra, edges with two equivalent Ti(4)N5O octahedra, edges with three equivalent Ti(2)N6 octahedra, and edges with four equivalent Ti(3)N6 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. In the fourth Ti site, Ti(4) is bonded to one N(4), two equivalent N(1), two equivalent N(3), and one O(2) atom to form TiN5O octahedra that share corners with two equivalent Ti(2)N6 octahedra, edges with two equivalent Ti(4)N5O octahedra, edges with two equivalent Ti(3)N6 octahedra, edges with two equivalent Ti(1)NO5 octahedra, and edges with three equivalent Ti(2)N6 octahedra. The corner-sharing octahedral tilt angles are 6°. There are four inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), and two equivalent Ti(4) atoms. In the second N site, N(2) is bonded in a rectangular see-saw-like geometry to one Ti(2) and three equivalent Ti(3) atoms. In the third N site, N(3) is bonded to one Ti(3), two equivalent Ti(2), and two equivalent Ti(4) atoms to form a mixture of corner and edge-sharing NTi5 square pyramids. In the fourth N site, N(4) is bonded to one Ti(4), two equivalent Ti(2), and two equivalent Ti(3) atoms to form a mixture of corner and edge-sharing NTi5 square pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(4) and two equivalent Ti(1) atoms.
Ti2N2O crystallizes in the monoclinic C2/m space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one N(1), two equivalent O(2), and three equivalent O(1) atoms to form TiNO5 octahedra that share  a cornercorner with one Ti(2)N6 octahedra, edges with two equivalent Ti(4)N5O octahedra, and edges with four equivalent Ti(1)NO5 octahedra. The corner-sharing octahedral tilt angles are 18°. The Ti(1)-N(1) bond length is 2.00 Å. Both Ti(1)-O(2) bond lengths are 2.03 Å. There are two shorter (1.94 Å) and one longer (2.09 Å) Ti(1)-O(1) bond length. In the second Ti site, Ti(2) is bonded to one N(1), one N(2), two equivalent N(3), and two equivalent N(4) atoms to form TiN6 octahedra that share  a cornercorner with one Ti(1)NO5 octahedra, corners with two equivalent Ti(4)N5O octahedra, corners with three equivalent Ti(3)N6 octahedra, edges with two equivalent Ti(2)N6 octahedra, edges with three equivalent Ti(4)N5O octahedra, and edges with three equivalent Ti(3)N6 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. The Ti(2)-N(1) bond length is 2.05 Å. The Ti(2)-N(2) bond length is 2.06 Å. Both Ti(2)-N(3) bond lengths are 2.09 Å. Both Ti(2)-N(4) bond lengths are 2.09 Å. In the third Ti site, Ti(3) is bonded to one N(3), two equivalent N(4), and three equivalent N(2) atoms to form TiN6 octahedra that share corners with three equivalent Ti(2)N6 octahedra, edges with two equivalent Ti(4)N5O octahedra, edges with three equivalent Ti(2)N6 octahedra, and edges with four equivalent Ti(3)N6 octahedra. The corner-sharing octahedral tilt angles range from 6-20°. The Ti(3)-N(3) bond length is 2.21 Å. Both Ti(3)-N(4) bond lengths are 2.14 Å. There is one shorter (1.96 Å) and two longer (2.02 Å) Ti(3)-N(2) bond lengths. In the fourth Ti site, Ti(4) is bonded to one N(4), two equivalent N(1), two equivalent N(3), and one O(2) atom to form TiN5O octahedra that share corners with two equivalent Ti(2)N6 octahedra, edges with two equivalent Ti(4)N5O octahedra, edges with two equivalent Ti(3)N6 octahedra, edges with two equivalent Ti(1)NO5 octahedra, and edges with three equivalent Ti(2)N6 octahedra. The corner-sharing octahedral tilt angles are 6°. The Ti(4)-N(4) bond length is 2.19 Å. Both Ti(4)-N(1) bond lengths are 2.02 Å. Both Ti(4)-N(3) bond lengths are 2.13 Å. The Ti(4)-O(2) bond length is 1.90 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), and two equivalent Ti(4) atoms. In the second N site, N(2) is bonded in a rectangular see-saw-like geometry to one Ti(2) and three equivalent Ti(3) atoms. In the third N site, N(3) is bonded to one Ti(3), two equivalent Ti(2), and two equivalent Ti(4) atoms to form a mixture of corner and edge-sharing NTi5 square pyramids. In the fourth N site, N(4) is bonded to one Ti(4), two equivalent Ti(2), and two equivalent Ti(3) atoms to form a mixture of corner and edge-sharing NTi5 square pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(4) and two equivalent Ti(1) atoms.