Ti(VN)4 crystallizes in the triclinic P-1 space group. Ti(1) is bonded in a rectangular see-saw-like geometry to one N(1), one N(2), one N(3), and one N(4) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form a mixture of distorted edge and corner-sharing VN4 tetrahedra. In the second V site, V(2) is bonded in a 4-coordinate geometry to two equivalent N(2) and two equivalent N(3) atoms. In the third V site, V(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form VN5 square pyramids that share corners with three equivalent V(4)N5 square pyramids,  a cornercorner with one V(1)N4 tetrahedra, edges with two equivalent V(3)N5 square pyramids, edges with three equivalent V(4)N5 square pyramids, and edges with two equivalent V(1)N4 tetrahedra. In the fourth V site, V(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form VN5 square pyramids that share corners with three equivalent V(3)N5 square pyramids, corners with three equivalent V(1)N4 tetrahedra, edges with two equivalent V(4)N5 square pyramids, edges with three equivalent V(3)N5 square pyramids, and  an edgeedge with one V(1)N4 tetrahedra. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ti(1), one V(1), two equivalent V(3), and two equivalent V(4) atoms to form NTiV5 octahedra that share corners with two equivalent N(3)TiV5 octahedra, corners with two equivalent N(4)TiV5 octahedra, corners with two equivalent N(2)TiV3 trigonal pyramids, edges with two equivalent N(1)TiV5 octahedra, edges with two equivalent N(3)TiV5 octahedra, and edges with four equivalent N(4)TiV5 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second N site, N(2) is bonded to one Ti(1), one V(1), and two equivalent V(2) atoms to form NTiV3 trigonal pyramids that share corners with two equivalent N(1)TiV5 octahedra, corners with two equivalent N(4)TiV5 octahedra, corners with six equivalent N(3)TiV5 octahedra, and  an edgeedge with one N(2)TiV3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 47-72°. In the third N site, N(3) is bonded to one Ti(1), one V(1), one V(3), one V(4), and two equivalent V(2) atoms to form NTiV5 octahedra that share corners with two equivalent N(1)TiV5 octahedra, corners with six equivalent N(2)TiV3 trigonal pyramids,  an edgeedge with one N(3)TiV5 octahedra, edges with two equivalent N(1)TiV5 octahedra, and edges with three equivalent N(4)TiV5 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the fourth N site, N(4) is bonded to one Ti(1), one V(1), two equivalent V(3), and two equivalent V(4) atoms to form NTiV5 octahedra that share corners with two equivalent N(1)TiV5 octahedra, corners with two equivalent N(2)TiV3 trigonal pyramids, edges with two equivalent N(4)TiV5 octahedra, edges with three equivalent N(3)TiV5 octahedra, and edges with four equivalent N(1)TiV5 octahedra. The corner-sharing octahedral tilt angles range from 3-6°.
Ti(VN)4 crystallizes in the triclinic P-1 space group. Ti(1) is bonded in a rectangular see-saw-like geometry to one N(1), one N(2), one N(3), and one N(4) atom. The Ti(1)-N(1) bond length is 2.04 Å. The Ti(1)-N(2) bond length is 1.93 Å. The Ti(1)-N(3) bond length is 2.06 Å. The Ti(1)-N(4) bond length is 2.02 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form a mixture of distorted edge and corner-sharing VN4 tetrahedra. The V(1)-N(1) bond length is 1.99 Å. The V(1)-N(2) bond length is 1.87 Å. The V(1)-N(3) bond length is 2.01 Å. The V(1)-N(4) bond length is 1.95 Å. In the second V site, V(2) is bonded in a 4-coordinate geometry to two equivalent N(2) and two equivalent N(3) atoms. There is one shorter (1.93 Å) and one longer (1.96 Å) V(2)-N(2) bond length. There is one shorter (2.03 Å) and one longer (2.06 Å) V(2)-N(3) bond length. In the third V site, V(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form VN5 square pyramids that share corners with three equivalent V(4)N5 square pyramids,  a cornercorner with one V(1)N4 tetrahedra, edges with two equivalent V(3)N5 square pyramids, edges with three equivalent V(4)N5 square pyramids, and edges with two equivalent V(1)N4 tetrahedra. The V(3)-N(3) bond length is 2.13 Å. There is one shorter (2.05 Å) and one longer (2.09 Å) V(3)-N(1) bond length. There is one shorter (2.05 Å) and one longer (2.10 Å) V(3)-N(4) bond length. In the fourth V site, V(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form VN5 square pyramids that share corners with three equivalent V(3)N5 square pyramids, corners with three equivalent V(1)N4 tetrahedra, edges with two equivalent V(4)N5 square pyramids, edges with three equivalent V(3)N5 square pyramids, and  an edgeedge with one V(1)N4 tetrahedra. The V(4)-N(3) bond length is 2.12 Å. Both V(4)-N(1) bond lengths are 2.07 Å. There is one shorter (2.01 Å) and one longer (2.08 Å) V(4)-N(4) bond length. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Ti(1), one V(1), two equivalent V(3), and two equivalent V(4) atoms to form NTiV5 octahedra that share corners with two equivalent N(3)TiV5 octahedra, corners with two equivalent N(4)TiV5 octahedra, corners with two equivalent N(2)TiV3 trigonal pyramids, edges with two equivalent N(1)TiV5 octahedra, edges with two equivalent N(3)TiV5 octahedra, and edges with four equivalent N(4)TiV5 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the second N site, N(2) is bonded to one Ti(1), one V(1), and two equivalent V(2) atoms to form NTiV3 trigonal pyramids that share corners with two equivalent N(1)TiV5 octahedra, corners with two equivalent N(4)TiV5 octahedra, corners with six equivalent N(3)TiV5 octahedra, and  an edgeedge with one N(2)TiV3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 47-72°. In the third N site, N(3) is bonded to one Ti(1), one V(1), one V(3), one V(4), and two equivalent V(2) atoms to form NTiV5 octahedra that share corners with two equivalent N(1)TiV5 octahedra, corners with six equivalent N(2)TiV3 trigonal pyramids,  an edgeedge with one N(3)TiV5 octahedra, edges with two equivalent N(1)TiV5 octahedra, and edges with three equivalent N(4)TiV5 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the fourth N site, N(4) is bonded to one Ti(1), one V(1), two equivalent V(3), and two equivalent V(4) atoms to form NTiV5 octahedra that share corners with two equivalent N(1)TiV5 octahedra, corners with two equivalent N(2)TiV3 trigonal pyramids, edges with two equivalent N(4)TiV5 octahedra, edges with three equivalent N(3)TiV5 octahedra, and edges with four equivalent N(1)TiV5 octahedra. The corner-sharing octahedral tilt angles range from 3-6°.