V(FeN)4 crystallizes in the triclinic P-1 space group. V(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted VN4 tetrahedra that share  a cornercorner with one Fe(4)N5 square pyramid, corners with three equivalent Fe(3)N5 square pyramids, corners with four equivalent Fe(1)N4 tetrahedra,  an edgeedge with one Fe(3)N5 square pyramid, and edges with two equivalent Fe(4)N5 square pyramids. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted FeN4 tetrahedra that share  a cornercorner with one Fe(3)N5 square pyramid, corners with three equivalent Fe(4)N5 square pyramids, corners with four equivalent V(1)N4 tetrahedra,  an edgeedge with one Fe(4)N5 square pyramid, and edges with two equivalent Fe(3)N5 square pyramids. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to two equivalent N(2) and two equivalent N(3) atoms. In the third Fe site, Fe(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form FeN5 square pyramids that share corners with three equivalent Fe(4)N5 square pyramids,  a cornercorner with one Fe(1)N4 tetrahedra, corners with three equivalent V(1)N4 tetrahedra, edges with two equivalent Fe(3)N5 square pyramids, edges with three equivalent Fe(4)N5 square pyramids,  an edgeedge with one V(1)N4 tetrahedra, and edges with two equivalent Fe(1)N4 tetrahedra. In the fourth Fe site, Fe(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form FeN5 square pyramids that share corners with three equivalent Fe(3)N5 square pyramids,  a cornercorner with one V(1)N4 tetrahedra, corners with three equivalent Fe(1)N4 tetrahedra, edges with two equivalent Fe(4)N5 square pyramids, edges with three equivalent Fe(3)N5 square pyramids,  an edgeedge with one Fe(1)N4 tetrahedra, and edges with two equivalent V(1)N4 tetrahedra. There are four inequivalent N sites. In the first N site, N(1) is bonded to one V(1), one Fe(1), two equivalent Fe(3), and two equivalent Fe(4) atoms to form NVFe5 octahedra that share corners with two equivalent N(3)VFe5 octahedra, corners with two equivalent N(4)VFe5 octahedra, corners with two equivalent N(2)VFe3 tetrahedra, edges with two equivalent N(1)VFe5 octahedra, edges with two equivalent N(3)VFe5 octahedra, and edges with four equivalent N(4)VFe5 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the second N site, N(2) is bonded to one V(1), one Fe(1), and two equivalent Fe(2) atoms to form NVFe3 tetrahedra that share corners with two equivalent N(1)VFe5 octahedra, corners with two equivalent N(4)VFe5 octahedra, corners with six equivalent N(3)VFe5 octahedra, and  an edgeedge with one N(2)VFe3 tetrahedra. The corner-sharing octahedral tilt angles range from 51-70°. In the third N site, N(3) is bonded to one V(1), one Fe(1), one Fe(3), one Fe(4), and two equivalent Fe(2) atoms to form NVFe5 octahedra that share corners with two equivalent N(1)VFe5 octahedra, corners with six equivalent N(2)VFe3 tetrahedra,  an edgeedge with one N(3)VFe5 octahedra, edges with two equivalent N(1)VFe5 octahedra, and edges with three equivalent N(4)VFe5 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the fourth N site, N(4) is bonded to one V(1), one Fe(1), two equivalent Fe(3), and two equivalent Fe(4) atoms to form NVFe5 octahedra that share corners with two equivalent N(1)VFe5 octahedra, corners with two equivalent N(2)VFe3 tetrahedra, edges with two equivalent N(4)VFe5 octahedra, edges with three equivalent N(3)VFe5 octahedra, and edges with four equivalent N(1)VFe5 octahedra. The corner-sharing octahedral tilt angles range from 7-8°.
V(FeN)4 crystallizes in the triclinic P-1 space group. V(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted VN4 tetrahedra that share  a cornercorner with one Fe(4)N5 square pyramid, corners with three equivalent Fe(3)N5 square pyramids, corners with four equivalent Fe(1)N4 tetrahedra,  an edgeedge with one Fe(3)N5 square pyramid, and edges with two equivalent Fe(4)N5 square pyramids. The V(1)-N(1) bond length is 1.93 Å. The V(1)-N(2) bond length is 1.88 Å. The V(1)-N(3) bond length is 1.92 Å. The V(1)-N(4) bond length is 1.91 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one N(1), one N(2), one N(3), and one N(4) atom to form distorted FeN4 tetrahedra that share  a cornercorner with one Fe(3)N5 square pyramid, corners with three equivalent Fe(4)N5 square pyramids, corners with four equivalent V(1)N4 tetrahedra,  an edgeedge with one Fe(4)N5 square pyramid, and edges with two equivalent Fe(3)N5 square pyramids. The Fe(1)-N(1) bond length is 1.95 Å. The Fe(1)-N(2) bond length is 1.83 Å. The Fe(1)-N(3) bond length is 1.87 Å. The Fe(1)-N(4) bond length is 1.94 Å. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to two equivalent N(2) and two equivalent N(3) atoms. Both Fe(2)-N(2) bond lengths are 1.88 Å. There is one shorter (1.93 Å) and one longer (1.94 Å) Fe(2)-N(3) bond length. In the third Fe site, Fe(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form FeN5 square pyramids that share corners with three equivalent Fe(4)N5 square pyramids,  a cornercorner with one Fe(1)N4 tetrahedra, corners with three equivalent V(1)N4 tetrahedra, edges with two equivalent Fe(3)N5 square pyramids, edges with three equivalent Fe(4)N5 square pyramids,  an edgeedge with one V(1)N4 tetrahedra, and edges with two equivalent Fe(1)N4 tetrahedra. The Fe(3)-N(3) bond length is 2.14 Å. There is one shorter (2.03 Å) and one longer (2.05 Å) Fe(3)-N(1) bond length. There is one shorter (2.03 Å) and one longer (2.24 Å) Fe(3)-N(4) bond length. In the fourth Fe site, Fe(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form FeN5 square pyramids that share corners with three equivalent Fe(3)N5 square pyramids,  a cornercorner with one V(1)N4 tetrahedra, corners with three equivalent Fe(1)N4 tetrahedra, edges with two equivalent Fe(4)N5 square pyramids, edges with three equivalent Fe(3)N5 square pyramids,  an edgeedge with one Fe(1)N4 tetrahedra, and edges with two equivalent V(1)N4 tetrahedra. The Fe(4)-N(3) bond length is 2.08 Å. There is one shorter (2.02 Å) and one longer (2.12 Å) Fe(4)-N(1) bond length. There is one shorter (2.01 Å) and one longer (2.28 Å) Fe(4)-N(4) bond length. There are four inequivalent N sites. In the first N site, N(1) is bonded to one V(1), one Fe(1), two equivalent Fe(3), and two equivalent Fe(4) atoms to form NVFe5 octahedra that share corners with two equivalent N(3)VFe5 octahedra, corners with two equivalent N(4)VFe5 octahedra, corners with two equivalent N(2)VFe3 tetrahedra, edges with two equivalent N(1)VFe5 octahedra, edges with two equivalent N(3)VFe5 octahedra, and edges with four equivalent N(4)VFe5 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the second N site, N(2) is bonded to one V(1), one Fe(1), and two equivalent Fe(2) atoms to form NVFe3 tetrahedra that share corners with two equivalent N(1)VFe5 octahedra, corners with two equivalent N(4)VFe5 octahedra, corners with six equivalent N(3)VFe5 octahedra, and  an edgeedge with one N(2)VFe3 tetrahedra. The corner-sharing octahedral tilt angles range from 51-70°. In the third N site, N(3) is bonded to one V(1), one Fe(1), one Fe(3), one Fe(4), and two equivalent Fe(2) atoms to form NVFe5 octahedra that share corners with two equivalent N(1)VFe5 octahedra, corners with six equivalent N(2)VFe3 tetrahedra,  an edgeedge with one N(3)VFe5 octahedra, edges with two equivalent N(1)VFe5 octahedra, and edges with three equivalent N(4)VFe5 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the fourth N site, N(4) is bonded to one V(1), one Fe(1), two equivalent Fe(3), and two equivalent Fe(4) atoms to form NVFe5 octahedra that share corners with two equivalent N(1)VFe5 octahedra, corners with two equivalent N(2)VFe3 tetrahedra, edges with two equivalent N(4)VFe5 octahedra, edges with three equivalent N(3)VFe5 octahedra, and edges with four equivalent N(1)VFe5 octahedra. The corner-sharing octahedral tilt angles range from 7-8°.