Na2BeCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Cl(1), one Cl(2), and four equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra, corners with four equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Na(2)Cl6 octahedra, and  an edgeedge with one Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-66°. In the second Na site, Na(2) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with two equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(2)Cl6 octahedra, and edges with two equivalent Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-66°. 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 Na(2)Cl6 octahedra, corners with four equivalent Na(1)Cl6 octahedra,  an edgeedge with one Na(1)Cl6 octahedra, and edges with two equivalent Na(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Be(1) atom. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Be(1) atom. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Be(1) atom.
Na2BeCl4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one Cl(1), one Cl(2), and four equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with four equivalent Na(2)Cl6 octahedra, corners with four equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Na(2)Cl6 octahedra, and  an edgeedge with one Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-66°. The Na(1)-Cl(1) bond length is 2.83 Å. The Na(1)-Cl(2) bond length is 2.75 Å. There are two shorter (2.81 Å) and two longer (2.82 Å) Na(1)-Cl(3) bond lengths. In the second Na site, Na(2) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form NaCl6 octahedra that share corners with four equivalent Na(1)Cl6 octahedra, corners with two equivalent Be(1)Cl4 tetrahedra, edges with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(2)Cl6 octahedra, and edges with two equivalent Be(1)Cl4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-66°. Both Na(2)-Cl(1) bond lengths are 2.83 Å. Both Na(2)-Cl(2) bond lengths are 2.72 Å. Both Na(2)-Cl(3) bond lengths are 2.78 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 Na(2)Cl6 octahedra, corners with four equivalent Na(1)Cl6 octahedra,  an edgeedge with one Na(1)Cl6 octahedra, and edges with two equivalent Na(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. The Be(1)-Cl(1) bond length is 2.01 Å. The Be(1)-Cl(2) bond length is 2.05 Å. Both Be(1)-Cl(3) bond lengths are 2.05 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Be(1) atom. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Be(1) atom. In the third Cl site, Cl(3) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one Be(1) atom.