Li2MnN2 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 trigonal pyramids that share corners with two equivalent Mn(1)N6 octahedra, corners with two equivalent Mn(2)N4 tetrahedra,  an edgeedge with one Mn(1)N6 octahedra, edges with two equivalent Mn(2)N4 tetrahedra, and  an edgeedge with one Li(2)N4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 12-67°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted MnN6 octahedra that share corners with four equivalent Li(2)N4 trigonal pyramids, edges with four equivalent Mn(2)N4 tetrahedra, and edges with two equivalent Li(2)N4 trigonal pyramids. In the second Mn site, Mn(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted MnN4 tetrahedra that share corners with two equivalent Li(2)N4 trigonal pyramids, edges with two equivalent Mn(1)N6 octahedra,  an edgeedge with one Mn(2)N4 tetrahedra, and edges with two equivalent Li(2)N4 trigonal pyramids. 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 Mn(1), and one Mn(2) atom. In the second N site, N(2) is bonded to two equivalent Li(1), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted edge and corner-sharing NLi4Mn3 pentagonal bipyramids.
Li2MnN2 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 2.39 Å. There are a spread of Li(1)-N(1) bond distances ranging from 2.05-2.48 Å. In the second Li site, Li(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form LiN4 trigonal pyramids that share corners with two equivalent Mn(1)N6 octahedra, corners with two equivalent Mn(2)N4 tetrahedra,  an edgeedge with one Mn(1)N6 octahedra, edges with two equivalent Mn(2)N4 tetrahedra, and  an edgeedge with one Li(2)N4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 12-67°. Both Li(2)-N(1) bond lengths are 2.08 Å. There is one shorter (1.94 Å) and one longer (1.99 Å) Li(2)-N(2) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent N(2) and four equivalent N(1) atoms to form distorted MnN6 octahedra that share corners with four equivalent Li(2)N4 trigonal pyramids, edges with four equivalent Mn(2)N4 tetrahedra, and edges with two equivalent Li(2)N4 trigonal pyramids. Both Mn(1)-N(2) bond lengths are 1.93 Å. All Mn(1)-N(1) bond lengths are 2.26 Å. In the second Mn site, Mn(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted MnN4 tetrahedra that share corners with two equivalent Li(2)N4 trigonal pyramids, edges with two equivalent Mn(1)N6 octahedra,  an edgeedge with one Mn(2)N4 tetrahedra, and edges with two equivalent Li(2)N4 trigonal pyramids. Both Mn(2)-N(1) bond lengths are 1.76 Å. Both Mn(2)-N(2) bond lengths are 1.90 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 Mn(1), and one Mn(2) atom. In the second N site, N(2) is bonded to two equivalent Li(1), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted edge and corner-sharing NLi4Mn3 pentagonal bipyramids.