LiCaAlN2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted LiN4 tetrahedra that share corners with six equivalent Ca(1)N6 octahedra, corners with two equivalent Li(1)N4 tetrahedra, corners with four equivalent Al(1)N4 tetrahedra, edges with three equivalent Ca(1)N6 octahedra,  an edgeedge with one Li(1)N4 tetrahedra, and edges with two equivalent Al(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-63°. Ca(1) is bonded to three equivalent N(1) and three equivalent N(2) atoms to form distorted CaN6 octahedra that share corners with six equivalent Li(1)N4 tetrahedra, corners with six equivalent Al(1)N4 tetrahedra, edges with six equivalent Ca(1)N6 octahedra, edges with three equivalent Li(1)N4 tetrahedra, and edges with three equivalent Al(1)N4 tetrahedra. Al(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form AlN4 tetrahedra that share corners with six equivalent Ca(1)N6 octahedra, corners with two equivalent Al(1)N4 tetrahedra, corners with four equivalent Li(1)N4 tetrahedra, edges with three equivalent Ca(1)N6 octahedra,  an edgeedge with one Al(1)N4 tetrahedra, and edges with two equivalent Li(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-61°. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), three equivalent Ca(1), and two equivalent Al(1) atoms. In the second N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), three equivalent Ca(1), and two equivalent Al(1) atoms.
LiCaAlN2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted LiN4 tetrahedra that share corners with six equivalent Ca(1)N6 octahedra, corners with two equivalent Li(1)N4 tetrahedra, corners with four equivalent Al(1)N4 tetrahedra, edges with three equivalent Ca(1)N6 octahedra,  an edgeedge with one Li(1)N4 tetrahedra, and edges with two equivalent Al(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-63°. There is one shorter (2.13 Å) and one longer (2.14 Å) Li(1)-N(1) bond length. There is one shorter (2.05 Å) and one longer (2.28 Å) Li(1)-N(2) bond length. Ca(1) is bonded to three equivalent N(1) and three equivalent N(2) atoms to form distorted CaN6 octahedra that share corners with six equivalent Li(1)N4 tetrahedra, corners with six equivalent Al(1)N4 tetrahedra, edges with six equivalent Ca(1)N6 octahedra, edges with three equivalent Li(1)N4 tetrahedra, and edges with three equivalent Al(1)N4 tetrahedra. There are a spread of Ca(1)-N(1) bond distances ranging from 2.47-2.65 Å. There are a spread of Ca(1)-N(2) bond distances ranging from 2.42-2.69 Å. Al(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form AlN4 tetrahedra that share corners with six equivalent Ca(1)N6 octahedra, corners with two equivalent Al(1)N4 tetrahedra, corners with four equivalent Li(1)N4 tetrahedra, edges with three equivalent Ca(1)N6 octahedra,  an edgeedge with one Al(1)N4 tetrahedra, and edges with two equivalent Li(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-61°. There is one shorter (1.92 Å) and one longer (1.97 Å) Al(1)-N(1) bond length. There is one shorter (1.94 Å) and one longer (1.95 Å) Al(1)-N(2) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), three equivalent Ca(1), and two equivalent Al(1) atoms. In the second N site, N(2) is bonded in a 7-coordinate geometry to two equivalent Li(1), three equivalent Ca(1), and two equivalent Al(1) atoms.