Li7VN4 crystallizes in the tetragonal P4_2/nmc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent N(1) atoms to form distorted LiN4 tetrahedra that share corners with four equivalent Li(3)N4 tetrahedra, corners with four equivalent V(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, edges with two equivalent Li(1)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. In the second Li site, Li(2) is bonded to four equivalent N(1) atoms to form LiN4 tetrahedra that share corners with two equivalent Li(3)N4 tetrahedra, corners with two equivalent V(1)N4 tetrahedra, corners with four equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra,  an edgeedge with one Li(3)N4 tetrahedra,  an edgeedge with one V(1)N4 tetrahedra, edges with two equivalent Li(1)N4 tetrahedra, and edges with two equivalent Li(2)N4 tetrahedra. In the third Li site, Li(3) is bonded to four equivalent N(1) atoms to form distorted LiN4 tetrahedra that share corners with eight equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, edges with two equivalent V(1)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. V(1) is bonded to four equivalent N(1) atoms to form VN4 tetrahedra that share corners with eight equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, edges with two equivalent Li(3)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. N(1) is bonded in a distorted body-centered cubic geometry to one Li(3), two equivalent Li(1), four equivalent Li(2), and one V(1) atom.
Li7VN4 crystallizes in the tetragonal P4_2/nmc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent N(1) atoms to form distorted LiN4 tetrahedra that share corners with four equivalent Li(3)N4 tetrahedra, corners with four equivalent V(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, edges with two equivalent Li(1)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. There are two shorter (2.11 Å) and two longer (2.37 Å) Li(1)-N(1) bond lengths. In the second Li site, Li(2) is bonded to four equivalent N(1) atoms to form LiN4 tetrahedra that share corners with two equivalent Li(3)N4 tetrahedra, corners with two equivalent V(1)N4 tetrahedra, corners with four equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra,  an edgeedge with one Li(3)N4 tetrahedra,  an edgeedge with one V(1)N4 tetrahedra, edges with two equivalent Li(1)N4 tetrahedra, and edges with two equivalent Li(2)N4 tetrahedra. There are two shorter (2.08 Å) and two longer (2.14 Å) Li(2)-N(1) bond lengths. In the third Li site, Li(3) is bonded to four equivalent N(1) atoms to form distorted LiN4 tetrahedra that share corners with eight equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, edges with two equivalent V(1)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. All Li(3)-N(1) bond lengths are 2.08 Å. V(1) is bonded to four equivalent N(1) atoms to form VN4 tetrahedra that share corners with eight equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, edges with two equivalent Li(3)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. All V(1)-N(1) bond lengths are 1.84 Å. N(1) is bonded in a distorted body-centered cubic geometry to one Li(3), two equivalent Li(1), four equivalent Li(2), and one V(1) atom.