Li2BeCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(1), one Cl(2), and four equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, corners with four equivalent Li(2)Cl6 octahedra, corners with four equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, and  an edgeedge with one Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. In the second Li site, Li(2) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, corners with two equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with two equivalent Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-58°. Be(1) is bonded to one Cl(1), one Cl(2), and two equivalent Cl(3) atoms to form BeCl4 tetrahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with four equivalent Li(1)Cl6 octahedra,  an edgeedge with one Li(1)Cl6 octahedra, and edges with two equivalent Li(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 56°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Be(1) atom. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Be(1) atom. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Be(1) atom.
Li2BeCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(1), one Cl(2), and four equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, corners with four equivalent Li(2)Cl6 octahedra, corners with four equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, and  an edgeedge with one Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-58°. The Li(1)-Cl(1) bond length is 2.65 Å. The Li(1)-Cl(2) bond length is 2.52 Å. All Li(1)-Cl(3) bond lengths are 2.57 Å. In the second Li site, Li(2) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form LiCl6 octahedra that share corners with four equivalent Li(1)Cl6 octahedra, corners with two equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Li(1)Cl6 octahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with two equivalent Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-58°. Both Li(2)-Cl(1) bond lengths are 2.59 Å. Both Li(2)-Cl(2) bond lengths are 2.48 Å. Both Li(2)-Cl(3) bond lengths are 2.53 Å. Be(1) is bonded to one Cl(1), one Cl(2), and two equivalent Cl(3) atoms to form BeCl4 tetrahedra that share corners with two equivalent Li(2)Cl6 octahedra, corners with four equivalent Li(1)Cl6 octahedra,  an edgeedge with one Li(1)Cl6 octahedra, and edges with two equivalent Li(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 56°. The Be(1)-Cl(1) bond length is 2.00 Å. The Be(1)-Cl(2) bond length is 2.05 Å. Both Be(1)-Cl(3) bond lengths are 2.04 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Be(1) atom. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Be(1) atom. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one Be(1) atom.