Li5ReN4 is Spinel-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form LiN4 tetrahedra that share corners with four equivalent Re(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. In the second Li site, Li(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted LiN4 tetrahedra that share corners with two equivalent Li(1)N4 tetrahedra, corners with two equivalent Re(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra,  an edgeedge with one Li(1)N4 tetrahedra,  an edgeedge with one Re(1)N4 tetrahedra, and edges with two equivalent Li(2)N4 tetrahedra. Re(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form ReN4 tetrahedra that share corners with four equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Li(1), four equivalent Li(2), and one Re(1) atom. In the second N site, N(2) is bonded to one Li(1), four equivalent Li(2), and one Re(1) atom to form a mixture of distorted edge and corner-sharing NLi5Re octahedra. The corner-sharing octahedral tilt angles range from 60-66°.
Li5ReN4 is Spinel-like structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form LiN4 tetrahedra that share corners with four equivalent Re(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. Both Li(1)-N(1) bond lengths are 2.10 Å. Both Li(1)-N(2) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted LiN4 tetrahedra that share corners with two equivalent Li(1)N4 tetrahedra, corners with two equivalent Re(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra,  an edgeedge with one Li(1)N4 tetrahedra,  an edgeedge with one Re(1)N4 tetrahedra, and edges with two equivalent Li(2)N4 tetrahedra. There is one shorter (2.04 Å) and one longer (2.18 Å) Li(2)-N(1) bond length. There is one shorter (2.06 Å) and one longer (2.14 Å) Li(2)-N(2) bond length. Re(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form ReN4 tetrahedra that share corners with four equivalent Li(1)N4 tetrahedra, corners with eight equivalent Li(2)N4 tetrahedra, and edges with four equivalent Li(2)N4 tetrahedra. Both Re(1)-N(1) bond lengths are 1.82 Å. Both Re(1)-N(2) bond lengths are 1.83 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Li(1), four equivalent Li(2), and one Re(1) atom. In the second N site, N(2) is bonded to one Li(1), four equivalent Li(2), and one Re(1) atom to form a mixture of distorted edge and corner-sharing NLi5Re octahedra. The corner-sharing octahedral tilt angles range from 60-66°.