Li5OsN4 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 distorted LiN4 tetrahedra that share corners with two equivalent Li(2)N4 tetrahedra, corners with two equivalent Os(1)N4 tetrahedra, corners with eight equivalent Li(1)N4 tetrahedra,  an edgeedge with one Li(2)N4 tetrahedra,  an edgeedge with one Os(1)N4 tetrahedra, and edges with two equivalent Li(1)N4 tetrahedra. In the second Li site, Li(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form LiN4 tetrahedra that share corners with four equivalent Os(1)N4 tetrahedra, corners with eight equivalent Li(1)N4 tetrahedra, and edges with four equivalent Li(1)N4 tetrahedra. Os(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form OsN4 tetrahedra that share corners with four equivalent Li(2)N4 tetrahedra, corners with eight equivalent Li(1)N4 tetrahedra, and edges with four equivalent Li(1)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(2), four equivalent Li(1), and one Os(1) atom. In the second N site, N(2) is bonded to one Li(2), four equivalent Li(1), and one Os(1) atom to form a mixture of edge and corner-sharing NLi5Os octahedra. The corner-sharing octahedral tilt angles range from 59-67°.
Li5OsN4 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 distorted LiN4 tetrahedra that share corners with two equivalent Li(2)N4 tetrahedra, corners with two equivalent Os(1)N4 tetrahedra, corners with eight equivalent Li(1)N4 tetrahedra,  an edgeedge with one Li(2)N4 tetrahedra,  an edgeedge with one Os(1)N4 tetrahedra, and edges with two equivalent Li(1)N4 tetrahedra. There is one shorter (2.07 Å) and one longer (2.20 Å) Li(1)-N(1) bond length. There is one shorter (2.10 Å) and one longer (2.15 Å) Li(1)-N(2) bond length. In the second Li site, Li(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form LiN4 tetrahedra that share corners with four equivalent Os(1)N4 tetrahedra, corners with eight equivalent Li(1)N4 tetrahedra, and edges with four equivalent Li(1)N4 tetrahedra. Both Li(2)-N(1) bond lengths are 2.14 Å. Both Li(2)-N(2) bond lengths are 2.09 Å. Os(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form OsN4 tetrahedra that share corners with four equivalent Li(2)N4 tetrahedra, corners with eight equivalent Li(1)N4 tetrahedra, and edges with four equivalent Li(1)N4 tetrahedra. Both Os(1)-N(1) bond lengths are 1.84 Å. Both Os(1)-N(2) bond lengths are 1.85 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Li(2), four equivalent Li(1), and one Os(1) atom. In the second N site, N(2) is bonded to one Li(2), four equivalent Li(1), and one Os(1) atom to form a mixture of edge and corner-sharing NLi5Os octahedra. The corner-sharing octahedral tilt angles range from 59-67°.