Na2Zr(WO4)3 crystallizes in the tetragonal I4_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with four equivalent W(3)O4 tetrahedra, and edges with two equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. In the second Na site, Na(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O4 tetrahedra, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. Zr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form ZrO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, and corners with two equivalent W(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-61°. There are three inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. In the second W site, W(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent Na(2)O6 octahedra and corners with four equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the third W site, W(3) is bonded to two equivalent O(2) and two equivalent O(5) atoms to form WO4 tetrahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Zr(1)O6 octahedra, and corners with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-74°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one W(3) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to one Zr(1) and one W(2) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Zr(1), one W(1), and one W(2) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Zr(1), and one W(3) atom. In the fifth O site, O(3) is bonded in a trigonal planar geometry to one Na(2), one W(1), and one W(2) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one W(1) atom.
Na2Zr(WO4)3 crystallizes in the tetragonal I4_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with four equivalent W(3)O4 tetrahedra, and edges with two equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. Both Na(1)-O(2) bond lengths are 2.72 Å. Both Na(1)-O(4) bond lengths are 2.50 Å. Both Na(1)-O(5) bond lengths are 2.29 Å. In the second Na site, Na(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O4 tetrahedra, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. Both Na(2)-O(3) bond lengths are 2.40 Å. Both Na(2)-O(4) bond lengths are 2.33 Å. Both Na(2)-O(5) bond lengths are 2.43 Å. Zr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form ZrO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, and corners with two equivalent W(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-61°. Both Zr(1)-O(1) bond lengths are 2.10 Å. Both Zr(1)-O(2) bond lengths are 2.14 Å. Both Zr(1)-O(6) bond lengths are 2.17 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. Both W(1)-O(1) bond lengths are 2.46 Å. Both W(1)-O(3) bond lengths are 1.93 Å. Both W(1)-O(4) bond lengths are 1.77 Å. In the second W site, W(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent Na(2)O6 octahedra and corners with four equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. Both W(2)-O(1) bond lengths are 1.98 Å. Both W(2)-O(3) bond lengths are 2.04 Å. Both W(2)-O(6) bond lengths are 1.87 Å. In the third W site, W(3) is bonded to two equivalent O(2) and two equivalent O(5) atoms to form WO4 tetrahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Zr(1)O6 octahedra, and corners with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-74°. Both W(3)-O(2) bond lengths are 1.86 Å. Both W(3)-O(5) bond lengths are 1.78 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one W(3) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to one Zr(1) and one W(2) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Zr(1), one W(1), and one W(2) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Zr(1), and one W(3) atom. In the fifth O site, O(3) is bonded in a trigonal planar geometry to one Na(2), one W(1), and one W(2) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one W(1) atom.