MgTi6(N2O3)2 crystallizes in the monoclinic Cm space group. Mg(1) is bonded in a 7-coordinate geometry to one N(3), two equivalent N(1), one O(3), one O(5), and two equivalent O(1) atoms. There are six inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one N(3), one N(4), one O(1), one O(4), and two equivalent O(2) atoms. In the second Ti site, Ti(2) is bonded to one N(1), two equivalent N(2), one O(4), one O(5), and one O(6) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(4)N2O4 octahedra, corners with two equivalent Ti(2)N3O3 octahedra,  an edgeedge with one Ti(3)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 18-39°. In the third Ti site, Ti(3) is bonded to one N(1), one N(3), one O(1), one O(5), and two equivalent O(3) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(6)N2O4 octahedra, corners with two equivalent Ti(3)N2O4 octahedra, corners with three equivalent Ti(5)N3O2 trigonal bipyramids,  an edgeedge with one Ti(2)N3O3 octahedra, and edges with two equivalent Ti(6)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 13-17°. In the fourth Ti site, Ti(4) is bonded to one N(2), one N(4), one O(2), one O(6), and two equivalent O(4) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(2)N3O3 octahedra, corners with two equivalent Ti(4)N2O4 octahedra,  an edgeedge with one Ti(6)N2O4 octahedra, edges with two equivalent Ti(2)N3O3 octahedra, and  an edgeedge with one Ti(5)N3O2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 18-35°. In the fifth Ti site, Ti(5) is bonded to one N(4), two equivalent N(3), one O(1), and one O(2) atom to form TiN3O2 trigonal bipyramids that share corners with three equivalent Ti(3)N2O4 octahedra, corners with two equivalent Ti(5)N3O2 trigonal bipyramids, and  an edgeedge with one Ti(4)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 14-68°. In the sixth Ti site, Ti(6) is bonded to one N(1), one N(2), one O(3), one O(6), and two equivalent O(5) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(3)N2O4 octahedra, corners with two equivalent Ti(6)N2O4 octahedra,  an edgeedge with one Ti(4)N2O4 octahedra, edges with two equivalent Ti(3)N2O4 octahedra, and edges with three equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 13-29°. There are four inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Mg(1), one Ti(2), one Ti(3), and one Ti(6) atom to form NMg2Ti3 trigonal bipyramids that share corners with two equivalent N(1)Mg2Ti3 trigonal bipyramids, corners with two equivalent O(1)Mg2Ti3 trigonal bipyramids, corners with three equivalent N(3)MgTi4 trigonal bipyramids, corners with three equivalent N(2)Ti4 trigonal pyramids, edges with three equivalent O(5)MgTi4 trigonal bipyramids, and  a faceface with one O(1)Mg2Ti3 trigonal bipyramid. In the second N site, N(2) is bonded to one Ti(4), one Ti(6), and two equivalent Ti(2) atoms to form NTi4 trigonal pyramids that share corners with three equivalent N(1)Mg2Ti3 trigonal bipyramids,  a cornercorner with one O(2)Ti4 trigonal pyramid, corners with two equivalent N(2)Ti4 trigonal pyramids, and edges with two equivalent O(5)MgTi4 trigonal bipyramids. In the third N site, N(3) is bonded to one Mg(1), one Ti(1), one Ti(3), and two equivalent Ti(5) atoms to form distorted NMgTi4 trigonal bipyramids that share corners with two equivalent N(3)MgTi4 trigonal bipyramids, corners with three equivalent N(1)Mg2Ti3 trigonal bipyramids,  an edgeedge with one O(5)MgTi4 trigonal bipyramid, edges with three equivalent O(1)Mg2Ti3 trigonal bipyramids, and edges with two equivalent O(2)Ti4 trigonal pyramids. In the fourth N site, N(4) is bonded in a T-shaped geometry to one Ti(1), one Ti(4), and one Ti(5) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), one Ti(1), one Ti(3), and one Ti(5) atom to form distorted OMg2Ti3 trigonal bipyramids that share corners with two equivalent N(1)Mg2Ti3 trigonal bipyramids, corners with two equivalent O(1)Mg2Ti3 trigonal bipyramids, corners with three equivalent O(5)MgTi4 trigonal bipyramids, corners with three equivalent O(2)Ti4 trigonal pyramids, edges with three equivalent N(3)MgTi4 trigonal bipyramids, and  a faceface with one N(1)Mg2Ti3 trigonal bipyramid. In the second O site, O(2) is bonded to one Ti(4), one Ti(5), and two equivalent Ti(1) atoms to form OTi4 trigonal pyramids that share corners with three equivalent O(1)Mg2Ti3 trigonal bipyramids,  a cornercorner with one N(2)Ti4 trigonal pyramid, corners with two equivalent O(2)Ti4 trigonal pyramids, and edges with two equivalent N(3)MgTi4 trigonal bipyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Mg(1), one Ti(6), and two equivalent Ti(3) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ti(1), one Ti(2), and two equivalent Ti(4) atoms. In the fifth O site, O(5) is bonded to one Mg(1), one Ti(2), one Ti(3), and two equivalent Ti(6) atoms to form distorted OMgTi4 trigonal bipyramids that share corners with two equivalent O(5)MgTi4 trigonal bipyramids, corners with three equivalent O(1)Mg2Ti3 trigonal bipyramids,  an edgeedge with one N(3)MgTi4 trigonal bipyramid, edges with three equivalent N(1)Mg2Ti3 trigonal bipyramids, and edges with two equivalent N(2)Ti4 trigonal pyramids. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Ti(2), one Ti(4), and one Ti(6) atom.
MgTi6(N2O3)2 crystallizes in the monoclinic Cm space group. Mg(1) is bonded in a 7-coordinate geometry to one N(3), two equivalent N(1), one O(3), one O(5), and two equivalent O(1) atoms. The Mg(1)-N(3) bond length is 2.33 Å. Both Mg(1)-N(1) bond lengths are 2.19 Å. The Mg(1)-O(3) bond length is 2.14 Å. The Mg(1)-O(5) bond length is 2.31 Å. Both Mg(1)-O(1) bond lengths are 2.54 Å. There are six inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one N(3), one N(4), one O(1), one O(4), and two equivalent O(2) atoms. The Ti(1)-N(3) bond length is 2.47 Å. The Ti(1)-N(4) bond length is 1.93 Å. The Ti(1)-O(1) bond length is 2.00 Å. The Ti(1)-O(4) bond length is 2.23 Å. Both Ti(1)-O(2) bond lengths are 1.99 Å. In the second Ti site, Ti(2) is bonded to one N(1), two equivalent N(2), one O(4), one O(5), and one O(6) atom to form distorted TiN3O3 octahedra that share  a cornercorner with one Ti(4)N2O4 octahedra, corners with two equivalent Ti(2)N3O3 octahedra,  an edgeedge with one Ti(3)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 18-39°. The Ti(2)-N(1) bond length is 1.95 Å. Both Ti(2)-N(2) bond lengths are 2.02 Å. The Ti(2)-O(4) bond length is 2.38 Å. The Ti(2)-O(5) bond length is 2.48 Å. The Ti(2)-O(6) bond length is 1.93 Å. In the third Ti site, Ti(3) is bonded to one N(1), one N(3), one O(1), one O(5), and two equivalent O(3) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(6)N2O4 octahedra, corners with two equivalent Ti(3)N2O4 octahedra, corners with three equivalent Ti(5)N3O2 trigonal bipyramids,  an edgeedge with one Ti(2)N3O3 octahedra, and edges with two equivalent Ti(6)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 13-17°. The Ti(3)-N(1) bond length is 2.30 Å. The Ti(3)-N(3) bond length is 1.97 Å. The Ti(3)-O(1) bond length is 1.92 Å. The Ti(3)-O(5) bond length is 2.07 Å. Both Ti(3)-O(3) bond lengths are 1.92 Å. In the fourth Ti site, Ti(4) is bonded to one N(2), one N(4), one O(2), one O(6), and two equivalent O(4) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(2)N3O3 octahedra, corners with two equivalent Ti(4)N2O4 octahedra,  an edgeedge with one Ti(6)N2O4 octahedra, edges with two equivalent Ti(2)N3O3 octahedra, and  an edgeedge with one Ti(5)N3O2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 18-35°. The Ti(4)-N(2) bond length is 2.11 Å. The Ti(4)-N(4) bond length is 1.96 Å. The Ti(4)-O(2) bond length is 2.16 Å. The Ti(4)-O(6) bond length is 2.04 Å. Both Ti(4)-O(4) bond lengths are 2.00 Å. In the fifth Ti site, Ti(5) is bonded to one N(4), two equivalent N(3), one O(1), and one O(2) atom to form TiN3O2 trigonal bipyramids that share corners with three equivalent Ti(3)N2O4 octahedra, corners with two equivalent Ti(5)N3O2 trigonal bipyramids, and  an edgeedge with one Ti(4)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 14-68°. The Ti(5)-N(4) bond length is 1.90 Å. Both Ti(5)-N(3) bond lengths are 2.05 Å. The Ti(5)-O(1) bond length is 1.96 Å. The Ti(5)-O(2) bond length is 2.11 Å. In the sixth Ti site, Ti(6) is bonded to one N(1), one N(2), one O(3), one O(6), and two equivalent O(5) atoms to form distorted TiN2O4 octahedra that share  a cornercorner with one Ti(3)N2O4 octahedra, corners with two equivalent Ti(6)N2O4 octahedra,  an edgeedge with one Ti(4)N2O4 octahedra, edges with two equivalent Ti(3)N2O4 octahedra, and edges with three equivalent Ti(2)N3O3 octahedra. The corner-sharing octahedral tilt angles range from 13-29°. The Ti(6)-N(1) bond length is 2.01 Å. The Ti(6)-N(2) bond length is 2.05 Å. The Ti(6)-O(3) bond length is 2.32 Å. The Ti(6)-O(6) bond length is 1.89 Å. Both Ti(6)-O(5) bond lengths are 1.97 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Mg(1), one Ti(2), one Ti(3), and one Ti(6) atom to form NMg2Ti3 trigonal bipyramids that share corners with two equivalent N(1)Mg2Ti3 trigonal bipyramids, corners with two equivalent O(1)Mg2Ti3 trigonal bipyramids, corners with three equivalent N(3)MgTi4 trigonal bipyramids, corners with three equivalent N(2)Ti4 trigonal pyramids, edges with three equivalent O(5)MgTi4 trigonal bipyramids, and  a faceface with one O(1)Mg2Ti3 trigonal bipyramid. In the second N site, N(2) is bonded to one Ti(4), one Ti(6), and two equivalent Ti(2) atoms to form NTi4 trigonal pyramids that share corners with three equivalent N(1)Mg2Ti3 trigonal bipyramids,  a cornercorner with one O(2)Ti4 trigonal pyramid, corners with two equivalent N(2)Ti4 trigonal pyramids, and edges with two equivalent O(5)MgTi4 trigonal bipyramids. In the third N site, N(3) is bonded to one Mg(1), one Ti(1), one Ti(3), and two equivalent Ti(5) atoms to form distorted NMgTi4 trigonal bipyramids that share corners with two equivalent N(3)MgTi4 trigonal bipyramids, corners with three equivalent N(1)Mg2Ti3 trigonal bipyramids,  an edgeedge with one O(5)MgTi4 trigonal bipyramid, edges with three equivalent O(1)Mg2Ti3 trigonal bipyramids, and edges with two equivalent O(2)Ti4 trigonal pyramids. In the fourth N site, N(4) is bonded in a T-shaped geometry to one Ti(1), one Ti(4), and one Ti(5) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), one Ti(1), one Ti(3), and one Ti(5) atom to form distorted OMg2Ti3 trigonal bipyramids that share corners with two equivalent N(1)Mg2Ti3 trigonal bipyramids, corners with two equivalent O(1)Mg2Ti3 trigonal bipyramids, corners with three equivalent O(5)MgTi4 trigonal bipyramids, corners with three equivalent O(2)Ti4 trigonal pyramids, edges with three equivalent N(3)MgTi4 trigonal bipyramids, and  a faceface with one N(1)Mg2Ti3 trigonal bipyramid. In the second O site, O(2) is bonded to one Ti(4), one Ti(5), and two equivalent Ti(1) atoms to form OTi4 trigonal pyramids that share corners with three equivalent O(1)Mg2Ti3 trigonal bipyramids,  a cornercorner with one N(2)Ti4 trigonal pyramid, corners with two equivalent O(2)Ti4 trigonal pyramids, and edges with two equivalent N(3)MgTi4 trigonal bipyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Mg(1), one Ti(6), and two equivalent Ti(3) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ti(1), one Ti(2), and two equivalent Ti(4) atoms. In the fifth O site, O(5) is bonded to one Mg(1), one Ti(2), one Ti(3), and two equivalent Ti(6) atoms to form distorted OMgTi4 trigonal bipyramids that share corners with two equivalent O(5)MgTi4 trigonal bipyramids, corners with three equivalent O(1)Mg2Ti3 trigonal bipyramids,  an edgeedge with one N(3)MgTi4 trigonal bipyramid, edges with three equivalent N(1)Mg2Ti3 trigonal bipyramids, and edges with two equivalent N(2)Ti4 trigonal pyramids. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Ti(2), one Ti(4), and one Ti(6) atom.