Li2Ca3N6 crystallizes in the orthorhombic Pmma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(6) atoms to form distorted face-sharing LiN6 octahedra. In the second Li site, Li(2) is bonded to two equivalent N(1), two equivalent N(4), and two equivalent N(5) atoms to form distorted face-sharing LiN6 octahedra. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to two equivalent N(1) and six equivalent N(5) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to two equivalent N(3) and six equivalent N(6) atoms. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one N(3), one N(4), one N(5), two equivalent N(1), and three equivalent N(2) atoms. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one N(1), one N(2), one N(6), two equivalent N(3), and three equivalent N(4) atoms. There are six inequivalent N sites. In the first N site, N(4) is bonded in a 7-coordinate geometry to two equivalent Li(2), one Ca(3), three equivalent Ca(4), and one N(3) atom. In the second N site, N(5) is bonded in a 7-coordinate geometry to two equivalent Li(2), one Ca(3), three equivalent Ca(1), and one N(5) atom. In the third N site, N(6) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(4), three equivalent Ca(2), and one N(6) atom. In the fourth N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Li(2), one Ca(1), one Ca(4), two equivalent Ca(3), and one N(2) atom. In the fifth N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(4), three equivalent Ca(3), and one N(1) atom. In the sixth N site, N(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(2), one Ca(3), two equivalent Ca(4), and one N(4) atom.
Li2Ca3N6 crystallizes in the orthorhombic Pmma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent N(2), two equivalent N(3), and two equivalent N(6) atoms to form distorted face-sharing LiN6 octahedra. Both Li(1)-N(2) bond lengths are 2.56 Å. Both Li(1)-N(3) bond lengths are 2.13 Å. Both Li(1)-N(6) bond lengths are 2.22 Å. In the second Li site, Li(2) is bonded to two equivalent N(1), two equivalent N(4), and two equivalent N(5) atoms to form distorted face-sharing LiN6 octahedra. Both Li(2)-N(1) bond lengths are 2.10 Å. Both Li(2)-N(4) bond lengths are 2.47 Å. Both Li(2)-N(5) bond lengths are 2.25 Å. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to two equivalent N(1) and six equivalent N(5) atoms. Both Ca(1)-N(1) bond lengths are 2.47 Å. There are two shorter (2.46 Å) and four longer (2.58 Å) Ca(1)-N(5) bond lengths. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to two equivalent N(3) and six equivalent N(6) atoms. Both Ca(2)-N(3) bond lengths are 2.49 Å. There are two shorter (2.45 Å) and four longer (2.59 Å) Ca(2)-N(6) bond lengths. In the third Ca site, Ca(3) is bonded in a 8-coordinate geometry to one N(3), one N(4), one N(5), two equivalent N(1), and three equivalent N(2) atoms. The Ca(3)-N(3) bond length is 2.37 Å. The Ca(3)-N(4) bond length is 2.53 Å. The Ca(3)-N(5) bond length is 2.47 Å. Both Ca(3)-N(1) bond lengths are 2.65 Å. There is one shorter (2.42 Å) and two longer (2.50 Å) Ca(3)-N(2) bond lengths. In the fourth Ca site, Ca(4) is bonded in a 8-coordinate geometry to one N(1), one N(2), one N(6), two equivalent N(3), and three equivalent N(4) atoms. The Ca(4)-N(1) bond length is 2.36 Å. The Ca(4)-N(2) bond length is 2.55 Å. The Ca(4)-N(6) bond length is 2.48 Å. Both Ca(4)-N(3) bond lengths are 2.64 Å. There is one shorter (2.44 Å) and two longer (2.52 Å) Ca(4)-N(4) bond lengths. There are six inequivalent N sites. In the first N site, N(4) is bonded in a 7-coordinate geometry to two equivalent Li(2), one Ca(3), three equivalent Ca(4), and one N(3) atom. The N(4)-N(3) bond length is 1.31 Å. In the second N site, N(5) is bonded in a 7-coordinate geometry to two equivalent Li(2), one Ca(3), three equivalent Ca(1), and one N(5) atom. The N(5)-N(5) bond length is 1.31 Å. In the third N site, N(6) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(4), three equivalent Ca(2), and one N(6) atom. The N(6)-N(6) bond length is 1.32 Å. In the fourth N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Li(2), one Ca(1), one Ca(4), two equivalent Ca(3), and one N(2) atom. The N(1)-N(2) bond length is 1.30 Å. In the fifth N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(4), three equivalent Ca(3), and one N(1) atom. In the sixth N site, N(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(2), one Ca(3), two equivalent Ca(4), and one N(4) atom.