Na2LiBe2F7 crystallizes in the tetragonal P-42_1m space group. Na(1) is bonded in a 8-coordinate geometry to one F(2), three equivalent F(3), and four equivalent F(1) atoms. Li(1) is bonded to four equivalent F(1) atoms to form LiF4 tetrahedra that share corners with four equivalent Be(1)F4 tetrahedra. Be(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form BeF4 tetrahedra that share  a cornercorner with one Be(1)F4 tetrahedra and corners with two equivalent Li(1)F4 tetrahedra. 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 in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Be(1) atoms. In the third F site, F(3) is bonded in a distorted single-bond geometry to three equivalent Na(1) and one Be(1) atom.
Na2LiBe2F7 crystallizes in the tetragonal P-42_1m space group. Na(1) is bonded in a 8-coordinate geometry to one F(2), three equivalent F(3), and four equivalent F(1) atoms. The Na(1)-F(2) bond length is 2.42 Å. There is one shorter (2.44 Å) and two longer (2.70 Å) Na(1)-F(3) bond lengths. There are two shorter (2.38 Å) and two longer (2.67 Å) Na(1)-F(1) bond lengths. Li(1) is bonded to four equivalent F(1) atoms to form LiF4 tetrahedra that share corners with four equivalent Be(1)F4 tetrahedra. All Li(1)-F(1) bond lengths are 1.87 Å. Be(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form BeF4 tetrahedra that share  a cornercorner with one Be(1)F4 tetrahedra and corners with two equivalent Li(1)F4 tetrahedra. The Be(1)-F(2) bond length is 1.62 Å. The Be(1)-F(3) bond length is 1.53 Å. Both Be(1)-F(1) bond lengths are 1.56 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 in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Be(1) atoms. In the third F site, F(3) is bonded in a distorted single-bond geometry to three equivalent Na(1) and one Be(1) atom.