V(NiN)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 Ni(4)N5 square pyramid and edges with two equivalent Ni(4)N5 square pyramids. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted T-shaped geometry to one N(2), one N(3), and one N(4) atom. In the second Ni site, Ni(2) is bonded in a distorted trigonal planar geometry to one N(3) and two equivalent N(2) atoms. In the third Ni site, Ni(3) is bonded in a square co-planar geometry to one N(3), one N(4), and two equivalent N(1) atoms. In the fourth Ni site, Ni(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form NiN5 square pyramids that share  a cornercorner with one V(1)N4 tetrahedra, edges with two equivalent Ni(4)N5 square pyramids, 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), two equivalent Ni(3), and two equivalent Ni(4) atoms to form NVNi4 trigonal bipyramids that share  a cornercorner with one N(2)VNi3 tetrahedra, corners with three equivalent N(3)VNi4 trigonal bipyramids, corners with three equivalent N(4)VNi4 trigonal bipyramids,  an edgeedge with one N(3)VNi4 trigonal bipyramid, edges with two equivalent N(1)VNi4 trigonal bipyramids, and edges with two equivalent N(4)VNi4 trigonal bipyramids. In the second N site, N(2) is bonded to one V(1), one Ni(1), and two equivalent Ni(2) atoms to form NVNi3 tetrahedra that share  a cornercorner with one N(1)VNi4 trigonal bipyramid, corners with two equivalent N(4)VNi4 trigonal bipyramids, corners with four equivalent N(3)VNi4 trigonal bipyramids, and  an edgeedge with one N(2)VNi3 tetrahedra. In the third N site, N(3) is bonded to one V(1), one Ni(1), one Ni(2), one Ni(3), and one Ni(4) atom to form NVNi4 trigonal bipyramids that share corners with four equivalent N(2)VNi3 tetrahedra,  a cornercorner with one N(4)VNi4 trigonal bipyramid, corners with three equivalent N(1)VNi4 trigonal bipyramids,  an edgeedge with one N(1)VNi4 trigonal bipyramid, and edges with two equivalent N(4)VNi4 trigonal bipyramids. In the fourth N site, N(4) is bonded to one V(1), one Ni(1), one Ni(3), and two equivalent Ni(4) atoms to form NVNi4 trigonal bipyramids that share corners with two equivalent N(2)VNi3 tetrahedra,  a cornercorner with one N(3)VNi4 trigonal bipyramid, corners with three equivalent N(1)VNi4 trigonal bipyramids,  an edgeedge with one N(4)VNi4 trigonal bipyramid, edges with two equivalent N(1)VNi4 trigonal bipyramids, and edges with two equivalent N(3)VNi4 trigonal bipyramids.
V(NiN)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 Ni(4)N5 square pyramid and edges with two equivalent Ni(4)N5 square pyramids. The V(1)-N(1) bond length is 1.91 Å. The V(1)-N(2) bond length is 1.84 Å. The V(1)-N(3) bond length is 1.84 Å. The V(1)-N(4) bond length is 1.83 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted T-shaped geometry to one N(2), one N(3), and one N(4) atom. The Ni(1)-N(2) bond length is 1.81 Å. The Ni(1)-N(3) bond length is 1.87 Å. The Ni(1)-N(4) bond length is 1.89 Å. In the second Ni site, Ni(2) is bonded in a distorted trigonal planar geometry to one N(3) and two equivalent N(2) atoms. The Ni(2)-N(3) bond length is 1.89 Å. There is one shorter (1.87 Å) and one longer (1.89 Å) Ni(2)-N(2) bond length. In the third Ni site, Ni(3) is bonded in a square co-planar geometry to one N(3), one N(4), and two equivalent N(1) atoms. The Ni(3)-N(3) bond length is 2.03 Å. The Ni(3)-N(4) bond length is 1.89 Å. There is one shorter (1.91 Å) and one longer (1.98 Å) Ni(3)-N(1) bond length. In the fourth Ni site, Ni(4) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form NiN5 square pyramids that share  a cornercorner with one V(1)N4 tetrahedra, edges with two equivalent Ni(4)N5 square pyramids, and edges with two equivalent V(1)N4 tetrahedra. The Ni(4)-N(3) bond length is 2.02 Å. There is one shorter (2.00 Å) and one longer (2.01 Å) Ni(4)-N(1) bond length. There is one shorter (1.99 Å) and one longer (2.08 Å) Ni(4)-N(4) bond length. There are four inequivalent N sites. In the first N site, N(1) is bonded to one V(1), two equivalent Ni(3), and two equivalent Ni(4) atoms to form NVNi4 trigonal bipyramids that share  a cornercorner with one N(2)VNi3 tetrahedra, corners with three equivalent N(3)VNi4 trigonal bipyramids, corners with three equivalent N(4)VNi4 trigonal bipyramids,  an edgeedge with one N(3)VNi4 trigonal bipyramid, edges with two equivalent N(1)VNi4 trigonal bipyramids, and edges with two equivalent N(4)VNi4 trigonal bipyramids. In the second N site, N(2) is bonded to one V(1), one Ni(1), and two equivalent Ni(2) atoms to form NVNi3 tetrahedra that share  a cornercorner with one N(1)VNi4 trigonal bipyramid, corners with two equivalent N(4)VNi4 trigonal bipyramids, corners with four equivalent N(3)VNi4 trigonal bipyramids, and  an edgeedge with one N(2)VNi3 tetrahedra. In the third N site, N(3) is bonded to one V(1), one Ni(1), one Ni(2), one Ni(3), and one Ni(4) atom to form NVNi4 trigonal bipyramids that share corners with four equivalent N(2)VNi3 tetrahedra,  a cornercorner with one N(4)VNi4 trigonal bipyramid, corners with three equivalent N(1)VNi4 trigonal bipyramids,  an edgeedge with one N(1)VNi4 trigonal bipyramid, and edges with two equivalent N(4)VNi4 trigonal bipyramids. In the fourth N site, N(4) is bonded to one V(1), one Ni(1), one Ni(3), and two equivalent Ni(4) atoms to form NVNi4 trigonal bipyramids that share corners with two equivalent N(2)VNi3 tetrahedra,  a cornercorner with one N(3)VNi4 trigonal bipyramid, corners with three equivalent N(1)VNi4 trigonal bipyramids,  an edgeedge with one N(4)VNi4 trigonal bipyramid, edges with two equivalent N(1)VNi4 trigonal bipyramids, and edges with two equivalent N(3)VNi4 trigonal bipyramids.