Na6ZnO4 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(2) and four equivalent O(1) atoms. In the second Na site, Na(2) is bonded to one O(2) and three equivalent O(1) atoms to form distorted NaO4 trigonal pyramids that share corners with two equivalent Zn(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 trigonal pyramids, and  an edgeedge with one Zn(1)O4 tetrahedra. Zn(1) is bonded to one O(2) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with six equivalent Na(2)O4 trigonal pyramids and edges with three equivalent Na(2)O4 trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 8-coordinate geometry to three equivalent Na(2), four equivalent Na(1), and one Zn(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and one Zn(1) atom.
Na6ZnO4 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(2) and four equivalent O(1) atoms. The Na(1)-O(2) bond length is 2.31 Å. There are two shorter (2.41 Å) and two longer (2.69 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded to one O(2) and three equivalent O(1) atoms to form distorted NaO4 trigonal pyramids that share corners with two equivalent Zn(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 trigonal pyramids, and  an edgeedge with one Zn(1)O4 tetrahedra. The Na(2)-O(2) bond length is 2.51 Å. There are two shorter (2.30 Å) and one longer (2.34 Å) Na(2)-O(1) bond length. Zn(1) is bonded to one O(2) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with six equivalent Na(2)O4 trigonal pyramids and edges with three equivalent Na(2)O4 trigonal pyramids. The Zn(1)-O(2) bond length is 1.97 Å. All Zn(1)-O(1) bond lengths are 2.00 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 8-coordinate geometry to three equivalent Na(2), four equivalent Na(1), and one Zn(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to three equivalent Na(1), three equivalent Na(2), and one Zn(1) atom.