Li2Ca3N6 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted face-sharing LiN6 octahedra. There are two 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(3) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one N(3), three equivalent N(1), and four equivalent N(2) atoms. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(1), three equivalent Ca(2), and one N(2) atom. In the second N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), four equivalent Ca(2), and one N(1) atom. In the third N site, N(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(2), three equivalent Ca(1), and one N(3) atom.
Li2Ca3N6 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted face-sharing LiN6 octahedra. Both Li(1)-N(1) bond lengths are 2.11 Å. Both Li(1)-N(2) bond lengths are 2.54 Å. Both Li(1)-N(3) bond lengths are 2.22 Å. There are two 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(3) atoms. Both Ca(1)-N(1) bond lengths are 2.48 Å. There are two shorter (2.46 Å) and four longer (2.58 Å) Ca(1)-N(3) bond lengths. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to one N(3), three equivalent N(1), and four equivalent N(2) atoms. The Ca(2)-N(3) bond length is 2.48 Å. There is one shorter (2.37 Å) and two longer (2.65 Å) Ca(2)-N(1) bond lengths. There are a spread of Ca(2)-N(2) bond distances ranging from 2.42-2.56 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(1), three equivalent Ca(2), and one N(2) atom. The N(1)-N(2) bond length is 1.31 Å. In the second N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), four equivalent Ca(2), and one N(1) atom. In the third N site, N(3) is bonded in a 7-coordinate geometry to two equivalent Li(1), one Ca(2), three equivalent Ca(1), and one N(3) atom. The N(3)-N(3) bond length is 1.32 Å.