Na2BeO2 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the third Na site, Na(3) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form distorted NaO4 trigonal pyramids that share  a cornercorner with one Be(2)O4 tetrahedra, corners with two equivalent Na(3)O4 trigonal pyramids, and  an edgeedge with one Be(2)O4 tetrahedra. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(3), one O(4), and two equivalent O(2) atoms. There are two inequivalent Be sites. In the first Be site, Be(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(2), and one O(3) atom. In the second Be site, Be(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form BeO4 tetrahedra that share  a cornercorner with one Na(3)O4 trigonal pyramid,  an edgeedge with one Be(2)O4 tetrahedra, and  an edgeedge with one Na(3)O4 trigonal pyramid. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(4), two equivalent Na(3), and one Be(1) atom. In the second O site, O(4) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), and two equivalent Be(2) atoms. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), one Be(1), and one Be(2) atom. In the fourth O site, O(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), two equivalent Na(4), one Be(1), and one Be(2) atom.
Na2BeO2 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Na(1)-O(1) bond length is 2.67 Å. The Na(1)-O(2) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(4) bond length is 2.40 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Na(2)-O(1) bond length is 2.22 Å. The Na(2)-O(2) bond length is 2.39 Å. The Na(2)-O(3) bond length is 2.30 Å. The Na(2)-O(4) bond length is 2.31 Å. In the third Na site, Na(3) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form distorted NaO4 trigonal pyramids that share  a cornercorner with one Be(2)O4 tetrahedra, corners with two equivalent Na(3)O4 trigonal pyramids, and  an edgeedge with one Be(2)O4 tetrahedra. The Na(3)-O(1) bond length is 2.30 Å. The Na(3)-O(4) bond length is 2.39 Å. There is one shorter (2.25 Å) and one longer (2.27 Å) Na(3)-O(3) bond length. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(3), one O(4), and two equivalent O(2) atoms. The Na(4)-O(3) bond length is 2.31 Å. The Na(4)-O(4) bond length is 2.29 Å. There is one shorter (2.23 Å) and one longer (2.31 Å) Na(4)-O(2) bond length. There are two inequivalent Be sites. In the first Be site, Be(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(2), and one O(3) atom. The Be(1)-O(1) bond length is 1.58 Å. The Be(1)-O(2) bond length is 1.57 Å. The Be(1)-O(3) bond length is 1.52 Å. In the second Be site, Be(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form BeO4 tetrahedra that share  a cornercorner with one Na(3)O4 trigonal pyramid,  an edgeedge with one Be(2)O4 tetrahedra, and  an edgeedge with one Na(3)O4 trigonal pyramid. The Be(2)-O(1) bond length is 1.68 Å. The Be(2)-O(2) bond length is 1.69 Å. There is one shorter (1.64 Å) and one longer (1.65 Å) Be(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(3) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(4), two equivalent Na(3), and one Be(1) atom. In the second O site, O(4) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), and two equivalent Be(2) atoms. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), one Be(1), and one Be(2) atom. In the fourth O site, O(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), two equivalent Na(4), one Be(1), and one Be(2) atom.