Li6Ni2N3 crystallizes in the orthorhombic Amm2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one N(1) and two equivalent N(2) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one N(1) and two equivalent N(2) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one N(1) and two equivalent N(2) atoms. In the fourth Li site, Li(4) is bonded in a linear geometry to two equivalent N(1) atoms. Ni(1) is bonded in a linear geometry to two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and two equivalent Li(4) atoms to form distorted NLi7 pentagonal bipyramids that share corners with two equivalent N(2)Li5Ni2 pentagonal bipyramids, corners with two equivalent N(1)Li7 pentagonal bipyramids, and edges with four equivalent N(2)Li5Ni2 pentagonal bipyramids. In the second N site, N(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and two equivalent Ni(1) atoms to form distorted NLi5Ni2 pentagonal bipyramids that share  a cornercorner with one N(1)Li7 pentagonal bipyramid, corners with three equivalent N(2)Li5Ni2 pentagonal bipyramids, edges with two equivalent N(2)Li5Ni2 pentagonal bipyramids, and edges with two equivalent N(1)Li7 pentagonal bipyramids.
Li6Ni2N3 crystallizes in the orthorhombic Amm2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal planar geometry to one N(1) and two equivalent N(2) atoms. The Li(1)-N(1) bond length is 2.01 Å. There is one shorter (2.09 Å) and one longer (2.10 Å) Li(1)-N(2) bond length. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one N(1) and two equivalent N(2) atoms. The Li(2)-N(1) bond length is 2.05 Å. There is one shorter (2.14 Å) and one longer (2.46 Å) Li(2)-N(2) bond length. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one N(1) and two equivalent N(2) atoms. The Li(3)-N(1) bond length is 2.33 Å. Both Li(3)-N(2) bond lengths are 2.13 Å. In the fourth Li site, Li(4) is bonded in a linear geometry to two equivalent N(1) atoms. Both Li(4)-N(1) bond lengths are 1.76 Å. Ni(1) is bonded in a linear geometry to two equivalent N(2) atoms. Both Ni(1)-N(2) bond lengths are 1.76 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and two equivalent Li(4) atoms to form distorted NLi7 pentagonal bipyramids that share corners with two equivalent N(2)Li5Ni2 pentagonal bipyramids, corners with two equivalent N(1)Li7 pentagonal bipyramids, and edges with four equivalent N(2)Li5Ni2 pentagonal bipyramids. In the second N site, N(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and two equivalent Ni(1) atoms to form distorted NLi5Ni2 pentagonal bipyramids that share  a cornercorner with one N(1)Li7 pentagonal bipyramid, corners with three equivalent N(2)Li5Ni2 pentagonal bipyramids, edges with two equivalent N(2)Li5Ni2 pentagonal bipyramids, and edges with two equivalent N(1)Li7 pentagonal bipyramids.