Li2IrN2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one N(2) and three equivalent N(1) atoms. 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 two equivalent Ir(1)N6 octahedra,  an edgeedge with one Ir(1)N6 octahedra, and  an edgeedge with one Li(2)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-75°. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted IrN6 octahedra that share corners with four equivalent Li(2)N4 tetrahedra and edges with two equivalent Li(2)N4 tetrahedra. In the second Ir site, Ir(2) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Li(2), three equivalent Li(1), one Ir(1), and one Ir(2) atom. In the second N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(2), one Ir(1), and two equivalent Ir(2) atoms.
Li2IrN2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one N(2) and three equivalent N(1) atoms. The Li(1)-N(2) bond length is 2.40 Å. There are a spread of Li(1)-N(1) bond distances ranging from 2.02-2.14 Å. 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 two equivalent Ir(1)N6 octahedra,  an edgeedge with one Ir(1)N6 octahedra, and  an edgeedge with one Li(2)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-75°. Both Li(2)-N(1) bond lengths are 1.99 Å. There is one shorter (1.97 Å) and one longer (2.00 Å) Li(2)-N(2) bond length. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted IrN6 octahedra that share corners with four equivalent Li(2)N4 tetrahedra and edges with two equivalent Li(2)N4 tetrahedra. Both Ir(1)-N(2) bond lengths are 2.08 Å. All Ir(1)-N(1) bond lengths are 2.10 Å. In the second Ir site, Ir(2) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Ir(2)-N(1) bond lengths are 1.99 Å. Both Ir(2)-N(2) bond lengths are 2.15 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), three equivalent Li(1), one Ir(1), and one Ir(2) atom. In the second N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(2), one Ir(1), and two equivalent Ir(2) atoms.