LiAlCl4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one Cl(1), one Cl(4), two equivalent Cl(2), and two equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with two equivalent Al(1)Cl4 tetrahedra,  an edgeedge with one Li(1)Cl6 octahedra, and edges with two equivalent Al(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. Al(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form AlCl4 tetrahedra that share corners with two equivalent Li(1)Cl6 octahedra and edges with two equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in an L-shaped geometry to one Li(1) and one Al(1) atom. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Al(1) atom. In the third Cl site, Cl(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Al(1) atom. In the fourth Cl site, Cl(4) is bonded in a bent 120 degrees geometry to one Li(1) and one Al(1) atom.
LiAlCl4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one Cl(1), one Cl(4), two equivalent Cl(2), and two equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with two equivalent Li(1)Cl6 octahedra, corners with two equivalent Al(1)Cl4 tetrahedra,  an edgeedge with one Li(1)Cl6 octahedra, and edges with two equivalent Al(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The Li(1)-Cl(1) bond length is 2.45 Å. The Li(1)-Cl(4) bond length is 2.50 Å. There is one shorter (2.62 Å) and one longer (2.77 Å) Li(1)-Cl(2) bond length. There is one shorter (2.57 Å) and one longer (2.78 Å) Li(1)-Cl(3) bond length. Al(1) is bonded to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom to form AlCl4 tetrahedra that share corners with two equivalent Li(1)Cl6 octahedra and edges with two equivalent Li(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Al(1)-Cl(1) bond length is 2.14 Å. The Al(1)-Cl(2) bond length is 2.16 Å. The Al(1)-Cl(3) bond length is 2.16 Å. The Al(1)-Cl(4) bond length is 2.13 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in an L-shaped geometry to one Li(1) and one Al(1) atom. In the second Cl site, Cl(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one Al(1) atom. In the third Cl site, Cl(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one Al(1) atom. In the fourth Cl site, Cl(4) is bonded in a bent 120 degrees geometry to one Li(1) and one Al(1) atom.