Ti3N2O3 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one N(1), one N(2), one O(1), one O(3), and two equivalent O(4) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(6)N2O4 octahedra,  a cornercorner with one Ti(5)N3O3 octahedra, corners with two equivalent Ti(1)N2O4 octahedra,  an edgeedge with one Ti(2)N3O3 octahedra,  an edgeedge with one Ti(3)N3O3 octahedra, edges with two equivalent Ti(6)N2O4 octahedra, and edges with two equivalent Ti(5)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-36°. In the second Ti site, Ti(2) is bonded to one N(1), two equivalent N(4), one O(2), one O(3), and one O(5) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(4)N2O4 octahedra,  a cornercorner with one Ti(3)N3O3 octahedra, corners with two equivalent Ti(2)N3O3 octahedra,  an edgeedge with one Ti(1)N2O4 octahedra, edges with two equivalent Ti(4)N2O4 octahedra, and edges with three equivalent Ti(5)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-57°. In the third Ti site, Ti(3) is bonded to one N(2), two equivalent N(3), one O(1), one O(2), and one O(6) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(4)N2O4 octahedra,  a cornercorner with one Ti(2)N3O3 octahedra, corners with two equivalent Ti(3)N3O3 octahedra,  an edgeedge with one Ti(1)N2O4 octahedra, edges with two equivalent Ti(4)N2O4 octahedra, and edges with three equivalent Ti(6)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 18-57°. In the fourth Ti site, Ti(4) is bonded to one N(3), one N(4), one O(5), one O(6), and two equivalent O(2) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(2)N3O3 octahedra,  a cornercorner with one Ti(3)N3O3 octahedra, corners with two equivalent Ti(4)N2O4 octahedra,  an edgeedge with one Ti(6)N2O4 octahedra,  an edgeedge with one Ti(5)N3O3 octahedra, edges with two equivalent Ti(2)N3O3 octahedra, and edges with two equivalent Ti(3)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 18-29°. In the fifth Ti site, Ti(5) is bonded to one N(4), two equivalent N(1), one O(3), one O(4), and one O(5) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(1)N2O4 octahedra,  a cornercorner with one Ti(6)N2O4 octahedra, corners with two equivalent Ti(5)N3O3 octahedra,  an edgeedge with one Ti(4)N2O4 octahedra, edges with two equivalent Ti(1)N2O4 octahedra, and edges with three equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-56°. In the sixth Ti site, Ti(6) is bonded to one N(2), one N(3), one O(4), one O(6), and two equivalent O(1) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(1)N2O4 octahedra,  a cornercorner with one Ti(5)N3O3 octahedra, corners with two equivalent Ti(6)N2O4 octahedra,  an edgeedge with one Ti(4)N2O4 octahedra, edges with two equivalent Ti(1)N2O4 octahedra, and edges with three equivalent Ti(3)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 24-56°. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ti(1), one Ti(2), and two equivalent Ti(5) atoms to form NTi4 trigonal pyramids that share  a cornercorner with one O(1)Ti4 trigonal pyramid, corners with two equivalent N(1)Ti4 trigonal pyramids, edges with two equivalent N(4)Ti4 trigonal pyramids, and edges with two equivalent O(4)Ti4 trigonal pyramids. In the second N site, N(2) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(3), and one Ti(6) atom. In the third N site, N(3) is bonded to one Ti(4), one Ti(6), and two equivalent Ti(3) atoms to form NTi4 trigonal pyramids that share  a cornercorner with one N(4)Ti4 trigonal pyramid,  a cornercorner with one O(4)Ti4 trigonal pyramid, corners with two equivalent N(3)Ti4 trigonal pyramids, and edges with two equivalent O(1)Ti4 trigonal pyramids. In the fourth N site, N(4) is bonded to one Ti(4), one Ti(5), and two equivalent Ti(2) atoms to form NTi4 trigonal pyramids that share  a cornercorner with one N(3)Ti4 trigonal pyramid,  a cornercorner with one O(4)Ti4 trigonal pyramid, corners with two equivalent N(4)Ti4 trigonal pyramids, and edges with two equivalent N(1)Ti4 trigonal pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ti(1), one Ti(3), and two equivalent Ti(6) atoms to form OTi4 trigonal pyramids that share  a cornercorner with one N(1)Ti4 trigonal pyramid, corners with two equivalent O(1)Ti4 trigonal pyramids, edges with two equivalent N(3)Ti4 trigonal pyramids, and edges with two equivalent O(4)Ti4 trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Ti(2), one Ti(3), and two equivalent Ti(4) atoms. In the third O site, O(3) is bonded in a T-shaped geometry to one Ti(1), one Ti(2), and one Ti(5) atom. In the fourth O site, O(4) is bonded to one Ti(5), one Ti(6), and two equivalent Ti(1) atoms to form distorted OTi4 trigonal pyramids that share  a cornercorner with one N(3)Ti4 trigonal pyramid,  a cornercorner with one N(4)Ti4 trigonal pyramid, corners with two equivalent O(4)Ti4 trigonal pyramids, edges with two equivalent N(1)Ti4 trigonal pyramids, and edges with two equivalent O(1)Ti4 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Ti(2), one Ti(4), and one Ti(5) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Ti(3), one Ti(4), and one Ti(6) atom.
Ti3N2O3 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cm space group. There are six inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one N(1), one N(2), one O(1), one O(3), and two equivalent O(4) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(6)N2O4 octahedra,  a cornercorner with one Ti(5)N3O3 octahedra, corners with two equivalent Ti(1)N2O4 octahedra,  an edgeedge with one Ti(2)N3O3 octahedra,  an edgeedge with one Ti(3)N3O3 octahedra, edges with two equivalent Ti(6)N2O4 octahedra, and edges with two equivalent Ti(5)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-36°. The Ti(1)-N(1) bond length is 2.06 Å. The Ti(1)-N(2) bond length is 1.97 Å. The Ti(1)-O(1) bond length is 2.13 Å. The Ti(1)-O(3) bond length is 1.94 Å. Both Ti(1)-O(4) bond lengths are 2.01 Å. In the second Ti site, Ti(2) is bonded to one N(1), two equivalent N(4), one O(2), one O(3), and one O(5) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(4)N2O4 octahedra,  a cornercorner with one Ti(3)N3O3 octahedra, corners with two equivalent Ti(2)N3O3 octahedra,  an edgeedge with one Ti(1)N2O4 octahedra, edges with two equivalent Ti(4)N2O4 octahedra, and edges with three equivalent Ti(5)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-57°. The Ti(2)-N(1) bond length is 2.05 Å. Both Ti(2)-N(4) bond lengths are 1.98 Å. The Ti(2)-O(2) bond length is 2.20 Å. The Ti(2)-O(3) bond length is 1.97 Å. The Ti(2)-O(5) bond length is 1.98 Å. In the third Ti site, Ti(3) is bonded to one N(2), two equivalent N(3), one O(1), one O(2), and one O(6) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(4)N2O4 octahedra,  a cornercorner with one Ti(2)N3O3 octahedra, corners with two equivalent Ti(3)N3O3 octahedra,  an edgeedge with one Ti(1)N2O4 octahedra, edges with two equivalent Ti(4)N2O4 octahedra, and edges with three equivalent Ti(6)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 18-57°. The Ti(3)-N(2) bond length is 1.91 Å. Both Ti(3)-N(3) bond lengths are 2.01 Å. The Ti(3)-O(1) bond length is 2.21 Å. The Ti(3)-O(2) bond length is 2.27 Å. The Ti(3)-O(6) bond length is 1.90 Å. In the fourth Ti site, Ti(4) is bonded to one N(3), one N(4), one O(5), one O(6), and two equivalent O(2) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(2)N3O3 octahedra,  a cornercorner with one Ti(3)N3O3 octahedra, corners with two equivalent Ti(4)N2O4 octahedra,  an edgeedge with one Ti(6)N2O4 octahedra,  an edgeedge with one Ti(5)N3O3 octahedra, edges with two equivalent Ti(2)N3O3 octahedra, and edges with two equivalent Ti(3)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 18-29°. The Ti(4)-N(3) bond length is 1.99 Å. The Ti(4)-N(4) bond length is 2.04 Å. The Ti(4)-O(5) bond length is 2.05 Å. The Ti(4)-O(6) bond length is 2.01 Å. Both Ti(4)-O(2) bond lengths are 1.97 Å. In the fifth Ti site, Ti(5) is bonded to one N(4), two equivalent N(1), one O(3), one O(4), and one O(5) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(1)N2O4 octahedra,  a cornercorner with one Ti(6)N2O4 octahedra, corners with two equivalent Ti(5)N3O3 octahedra,  an edgeedge with one Ti(4)N2O4 octahedra, edges with two equivalent Ti(1)N2O4 octahedra, and edges with three equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 22-56°. The Ti(5)-N(4) bond length is 2.04 Å. Both Ti(5)-N(1) bond lengths are 1.99 Å. The Ti(5)-O(3) bond length is 1.99 Å. The Ti(5)-O(4) bond length is 2.33 Å. The Ti(5)-O(5) bond length is 1.92 Å. In the sixth Ti site, Ti(6) is bonded to one N(2), one N(3), one O(4), one O(6), and two equivalent O(1) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(1)N2O4 octahedra,  a cornercorner with one Ti(5)N3O3 octahedra, corners with two equivalent Ti(6)N2O4 octahedra,  an edgeedge with one Ti(4)N2O4 octahedra, edges with two equivalent Ti(1)N2O4 octahedra, and edges with three equivalent Ti(3)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 24-56°. The Ti(6)-N(2) bond length is 1.90 Å. The Ti(6)-N(3) bond length is 2.14 Å. The Ti(6)-O(4) bond length is 2.14 Å. The Ti(6)-O(6) bond length is 1.98 Å. Both Ti(6)-O(1) bond lengths are 1.98 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ti(1), one Ti(2), and two equivalent Ti(5) atoms to form NTi4 trigonal pyramids that share  a cornercorner with one O(1)Ti4 trigonal pyramid, corners with two equivalent N(1)Ti4 trigonal pyramids, edges with two equivalent N(4)Ti4 trigonal pyramids, and edges with two equivalent O(4)Ti4 trigonal pyramids. In the second N site, N(2) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(3), and one Ti(6) atom. In the third N site, N(3) is bonded to one Ti(4), one Ti(6), and two equivalent Ti(3) atoms to form NTi4 trigonal pyramids that share  a cornercorner with one N(4)Ti4 trigonal pyramid,  a cornercorner with one O(4)Ti4 trigonal pyramid, corners with two equivalent N(3)Ti4 trigonal pyramids, and edges with two equivalent O(1)Ti4 trigonal pyramids. In the fourth N site, N(4) is bonded to one Ti(4), one Ti(5), and two equivalent Ti(2) atoms to form NTi4 trigonal pyramids that share  a cornercorner with one N(3)Ti4 trigonal pyramid,  a cornercorner with one O(4)Ti4 trigonal pyramid, corners with two equivalent N(4)Ti4 trigonal pyramids, and edges with two equivalent N(1)Ti4 trigonal pyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Ti(1), one Ti(3), and two equivalent Ti(6) atoms to form OTi4 trigonal pyramids that share  a cornercorner with one N(1)Ti4 trigonal pyramid, corners with two equivalent O(1)Ti4 trigonal pyramids, edges with two equivalent N(3)Ti4 trigonal pyramids, and edges with two equivalent O(4)Ti4 trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Ti(2), one Ti(3), and two equivalent Ti(4) atoms. In the third O site, O(3) is bonded in a T-shaped geometry to one Ti(1), one Ti(2), and one Ti(5) atom. In the fourth O site, O(4) is bonded to one Ti(5), one Ti(6), and two equivalent Ti(1) atoms to form distorted OTi4 trigonal pyramids that share  a cornercorner with one N(3)Ti4 trigonal pyramid,  a cornercorner with one N(4)Ti4 trigonal pyramid, corners with two equivalent O(4)Ti4 trigonal pyramids, edges with two equivalent N(1)Ti4 trigonal pyramids, and edges with two equivalent O(1)Ti4 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Ti(2), one Ti(4), and one Ti(5) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Ti(3), one Ti(4), and one Ti(6) atom.