Na2BeF4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted NaF7 pentagonal bipyramids that share corners with four equivalent Na(2)F6 octahedra, corners with four equivalent Na(1)F7 pentagonal bipyramids,  a cornercorner with one Be(1)F4 tetrahedra, edges with three equivalent Na(2)F6 octahedra,  an edgeedge with one Na(1)F7 pentagonal bipyramid, and edges with three equivalent Be(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-69°. In the second Na site, Na(2) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted NaF6 octahedra that share corners with four equivalent Na(1)F7 pentagonal bipyramids, corners with four equivalent Be(1)F4 tetrahedra, edges with two equivalent Na(2)F6 octahedra, edges with three equivalent Na(1)F7 pentagonal bipyramids, and  an edgeedge with one Be(1)F4 tetrahedra. Be(1) is bonded to one F(1), one F(2), one F(3), and one F(4) atom to form BeF4 tetrahedra that share corners with four equivalent Na(2)F6 octahedra,  a cornercorner with one Na(1)F7 pentagonal bipyramid,  an edgeedge with one Na(2)F6 octahedra, and edges with three equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 5-50°. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Na(1), two equivalent Na(2), and one Be(1) atom to form a mixture of distorted corner and edge-sharing FNa4Be trigonal bipyramids. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one Be(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one Be(1) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Be(1) atom.
Na2BeF4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted NaF7 pentagonal bipyramids that share corners with four equivalent Na(2)F6 octahedra, corners with four equivalent Na(1)F7 pentagonal bipyramids,  a cornercorner with one Be(1)F4 tetrahedra, edges with three equivalent Na(2)F6 octahedra,  an edgeedge with one Na(1)F7 pentagonal bipyramid, and edges with three equivalent Be(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-69°. The Na(1)-F(4) bond length is 2.25 Å. There is one shorter (2.39 Å) and one longer (2.46 Å) Na(1)-F(1) bond length. There is one shorter (2.29 Å) and one longer (2.50 Å) Na(1)-F(2) bond length. There is one shorter (2.33 Å) and one longer (2.37 Å) Na(1)-F(3) bond length. In the second Na site, Na(2) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted NaF6 octahedra that share corners with four equivalent Na(1)F7 pentagonal bipyramids, corners with four equivalent Be(1)F4 tetrahedra, edges with two equivalent Na(2)F6 octahedra, edges with three equivalent Na(1)F7 pentagonal bipyramids, and  an edgeedge with one Be(1)F4 tetrahedra. The Na(2)-F(2) bond length is 2.24 Å. The Na(2)-F(3) bond length is 2.24 Å. There is one shorter (2.25 Å) and one longer (2.42 Å) Na(2)-F(1) bond length. There is one shorter (2.30 Å) and one longer (2.31 Å) Na(2)-F(4) bond length. Be(1) is bonded to one F(1), one F(2), one F(3), and one F(4) atom to form BeF4 tetrahedra that share corners with four equivalent Na(2)F6 octahedra,  a cornercorner with one Na(1)F7 pentagonal bipyramid,  an edgeedge with one Na(2)F6 octahedra, and edges with three equivalent Na(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 5-50°. The Be(1)-F(1) bond length is 1.56 Å. The Be(1)-F(2) bond length is 1.55 Å. The Be(1)-F(3) bond length is 1.54 Å. The Be(1)-F(4) bond length is 1.56 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Na(1), two equivalent Na(2), and one Be(1) atom to form a mixture of distorted corner and edge-sharing FNa4Be trigonal bipyramids. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one Be(1) atom. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one Be(1) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one Be(1) atom.