NaLiBeF4 is Ilmenite-derived structured and crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(2), one F(3), and four equivalent F(1) atoms to form distorted NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Be(1)F4 tetrahedra, edges with two equivalent Li(1)F6 octahedra, and  an edgeedge with one Be(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-65°. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with two equivalent Be(1)F4 tetrahedra, edges with two equivalent Na(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent Be(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-65°. Be(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form BeF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Na(1)F6 octahedra,  an edgeedge with one Na(1)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-64°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), and one Be(1) atom. In the second F site, F(2) is bonded to one Na(1), two equivalent Li(1), and one Be(1) atom to form distorted corner-sharing FNaLi2Be trigonal pyramids. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Li(1), and one Be(1) atom.
NaLiBeF4 is Ilmenite-derived structured and crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one F(2), one F(3), and four equivalent F(1) atoms to form distorted NaF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with four equivalent Li(1)F6 octahedra, corners with four equivalent Be(1)F4 tetrahedra, edges with two equivalent Li(1)F6 octahedra, and  an edgeedge with one Be(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-65°. The Na(1)-F(2) bond length is 2.29 Å. The Na(1)-F(3) bond length is 2.46 Å. There are two shorter (2.26 Å) and two longer (2.37 Å) Na(1)-F(1) bond lengths. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent Na(1)F6 octahedra, corners with two equivalent Be(1)F4 tetrahedra, edges with two equivalent Na(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent Be(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-65°. Both Li(1)-F(1) bond lengths are 2.08 Å. Both Li(1)-F(2) bond lengths are 2.04 Å. Both Li(1)-F(3) bond lengths are 2.17 Å. Be(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form BeF4 tetrahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent Na(1)F6 octahedra,  an edgeedge with one Na(1)F6 octahedra, and edges with two equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 47-64°. The Be(1)-F(2) bond length is 1.59 Å. The Be(1)-F(3) bond length is 1.55 Å. Both Be(1)-F(1) bond lengths are 1.57 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), and one Be(1) atom. In the second F site, F(2) is bonded to one Na(1), two equivalent Li(1), and one Be(1) atom to form distorted corner-sharing FNaLi2Be trigonal pyramids. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Li(1), and one Be(1) atom.