Na3Zn2(WO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to two equivalent O(4) and four equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(5) and four equivalent O(6) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded in a distorted tetrahedral geometry to two equivalent O(4) and two equivalent O(5) atoms. In the second W site, W(2) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(6) atom. Zn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one W(2) and one Zn(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one W(2), and one Zn(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one W(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(2), one W(1), and one Zn(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one W(1), and one Zn(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(3), one W(2), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing ONa2ZnW tetrahedra.
Na3Zn2(WO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Na(1)-O(2) bond lengths are 2.36 Å. Both Na(1)-O(3) bond lengths are 2.54 Å. Both Na(1)-O(5) bond lengths are 2.44 Å. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to two equivalent O(4) and four equivalent O(3) atoms. Both Na(2)-O(4) bond lengths are 2.56 Å. There are two shorter (2.41 Å) and two longer (2.69 Å) Na(2)-O(3) bond lengths. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(5) and four equivalent O(6) atoms. Both Na(3)-O(5) bond lengths are 2.92 Å. There are two shorter (2.41 Å) and two longer (2.56 Å) Na(3)-O(6) bond lengths. There are two inequivalent W sites. In the first W site, W(1) is bonded in a distorted tetrahedral geometry to two equivalent O(4) and two equivalent O(5) atoms. Both W(1)-O(4) bond lengths are 1.90 Å. Both W(1)-O(5) bond lengths are 1.90 Å. In the second W site, W(2) is bonded in a tetrahedral geometry to one O(1), one O(2), one O(3), and one O(6) atom. The W(2)-O(1) bond length is 1.83 Å. The W(2)-O(2) bond length is 1.82 Å. The W(2)-O(3) bond length is 1.78 Å. The W(2)-O(6) bond length is 1.84 Å. Zn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one O(6) atom. The Zn(1)-O(1) bond length is 2.29 Å. The Zn(1)-O(2) bond length is 2.12 Å. The Zn(1)-O(4) bond length is 1.98 Å. The Zn(1)-O(5) bond length is 2.00 Å. The Zn(1)-O(6) bond length is 2.19 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one W(2) and one Zn(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one W(2), and one Zn(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one W(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(2), one W(1), and one Zn(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one W(1), and one Zn(1) atom. In the sixth O site, O(6) is bonded to two equivalent Na(3), one W(2), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing ONa2ZnW tetrahedra.