Na6(WO3)7 crystallizes in the trigonal R-3 space group. Na(1) is bonded to two equivalent O(3), three equivalent O(1), three equivalent O(2), and four equivalent O(4) atoms to form NaO12 cuboctahedra that share corners with ten equivalent Na(1)O12 cuboctahedra, faces with five equivalent Na(1)O12 cuboctahedra,  a faceface with one W(2)O6 octahedra, and faces with seven equivalent W(1)O6 octahedra. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form WO6 octahedra that share  a cornercorner with one W(2)O6 octahedra, corners with five equivalent W(1)O6 octahedra, and faces with seven equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second W site, W(2) is bonded to six equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent W(1)O6 octahedra and faces with six equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. There are four inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Na(1) and two equivalent W(1) atoms to form distorted ONa3W2 square pyramids that share corners with five equivalent O(3)Na4W2 octahedra, corners with five equivalent O(4)Na4W2 octahedra, corners with two equivalent O(1)Na3W2 square pyramids, corners with seven equivalent O(2)Na3W2 square pyramids,  an edgeedge with one O(4)Na4W2 octahedra, edges with two equivalent O(2)Na3W2 square pyramids, edges with three equivalent O(1)Na3W2 square pyramids,  a faceface with one O(3)Na4W2 octahedra, and faces with three equivalent O(4)Na4W2 octahedra. The corner-sharing octahedral tilt angles range from 1-61°. In the second O site, O(2) is bonded to three equivalent Na(1), one W(1), and one W(2) atom to form distorted ONa3W2 square pyramids that share corners with two equivalent O(3)Na4W2 octahedra, corners with nine equivalent O(4)Na4W2 octahedra,  a cornercorner with one O(2)Na3W2 square pyramid, corners with seven equivalent O(1)Na3W2 square pyramids,  an edgeedge with one O(3)Na4W2 octahedra,  an edgeedge with one O(4)Na4W2 octahedra, edges with two equivalent O(1)Na3W2 square pyramids, edges with two equivalent O(2)Na3W2 square pyramids,  a faceface with one O(3)Na4W2 octahedra,  a faceface with one O(4)Na4W2 octahedra, and faces with two equivalent O(2)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 0-60°. In the third O site, O(3) is bonded to four equivalent Na(1) and two equivalent W(1) atoms to form distorted ONa4W2 octahedra that share corners with four equivalent O(3)Na4W2 octahedra, corners with four equivalent O(4)Na4W2 octahedra, corners with four equivalent O(2)Na3W2 square pyramids, corners with ten equivalent O(1)Na3W2 square pyramids, edges with two equivalent O(4)Na4W2 octahedra, edges with two equivalent O(2)Na3W2 square pyramids, faces with four equivalent O(4)Na4W2 octahedra, faces with two equivalent O(1)Na3W2 square pyramids, and faces with two equivalent O(2)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 0-60°. In the fourth O site, O(4) is bonded to four equivalent Na(1) and two equivalent W(1) atoms to form distorted ONa4W2 octahedra that share corners with two equivalent O(3)Na4W2 octahedra, corners with six equivalent O(4)Na4W2 octahedra, corners with five equivalent O(1)Na3W2 square pyramids, corners with nine equivalent O(2)Na3W2 square pyramids,  an edgeedge with one O(3)Na4W2 octahedra,  an edgeedge with one O(4)Na4W2 octahedra,  an edgeedge with one O(1)Na3W2 square pyramid,  an edgeedge with one O(2)Na3W2 square pyramid, faces with two equivalent O(3)Na4W2 octahedra, faces with two equivalent O(4)Na4W2 octahedra,  a faceface with one O(2)Na3W2 square pyramid, and faces with three equivalent O(1)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 0-60°.
Na6(WO3)7 crystallizes in the trigonal R-3 space group. Na(1) is bonded to two equivalent O(3), three equivalent O(1), three equivalent O(2), and four equivalent O(4) atoms to form NaO12 cuboctahedra that share corners with ten equivalent Na(1)O12 cuboctahedra, faces with five equivalent Na(1)O12 cuboctahedra,  a faceface with one W(2)O6 octahedra, and faces with seven equivalent W(1)O6 octahedra. Both Na(1)-O(3) bond lengths are 2.80 Å. There are a spread of Na(1)-O(1) bond distances ranging from 2.78-2.80 Å. There is one shorter (2.77 Å) and two longer (2.79 Å) Na(1)-O(2) bond lengths. All Na(1)-O(4) bond lengths are 2.80 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form WO6 octahedra that share  a cornercorner with one W(2)O6 octahedra, corners with five equivalent W(1)O6 octahedra, and faces with seven equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. The W(1)-O(2) bond length is 1.97 Å. The W(1)-O(3) bond length is 1.98 Å. There is one shorter (1.95 Å) and one longer (1.99 Å) W(1)-O(1) bond length. There is one shorter (1.99 Å) and one longer (2.00 Å) W(1)-O(4) bond length. In the second W site, W(2) is bonded to six equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent W(1)O6 octahedra and faces with six equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. All W(2)-O(2) bond lengths are 1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Na(1) and two equivalent W(1) atoms to form distorted ONa3W2 square pyramids that share corners with five equivalent O(3)Na4W2 octahedra, corners with five equivalent O(4)Na4W2 octahedra, corners with two equivalent O(1)Na3W2 square pyramids, corners with seven equivalent O(2)Na3W2 square pyramids,  an edgeedge with one O(4)Na4W2 octahedra, edges with two equivalent O(2)Na3W2 square pyramids, edges with three equivalent O(1)Na3W2 square pyramids,  a faceface with one O(3)Na4W2 octahedra, and faces with three equivalent O(4)Na4W2 octahedra. The corner-sharing octahedral tilt angles range from 1-61°. In the second O site, O(2) is bonded to three equivalent Na(1), one W(1), and one W(2) atom to form distorted ONa3W2 square pyramids that share corners with two equivalent O(3)Na4W2 octahedra, corners with nine equivalent O(4)Na4W2 octahedra,  a cornercorner with one O(2)Na3W2 square pyramid, corners with seven equivalent O(1)Na3W2 square pyramids,  an edgeedge with one O(3)Na4W2 octahedra,  an edgeedge with one O(4)Na4W2 octahedra, edges with two equivalent O(1)Na3W2 square pyramids, edges with two equivalent O(2)Na3W2 square pyramids,  a faceface with one O(3)Na4W2 octahedra,  a faceface with one O(4)Na4W2 octahedra, and faces with two equivalent O(2)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 0-60°. In the third O site, O(3) is bonded to four equivalent Na(1) and two equivalent W(1) atoms to form distorted ONa4W2 octahedra that share corners with four equivalent O(3)Na4W2 octahedra, corners with four equivalent O(4)Na4W2 octahedra, corners with four equivalent O(2)Na3W2 square pyramids, corners with ten equivalent O(1)Na3W2 square pyramids, edges with two equivalent O(4)Na4W2 octahedra, edges with two equivalent O(2)Na3W2 square pyramids, faces with four equivalent O(4)Na4W2 octahedra, faces with two equivalent O(1)Na3W2 square pyramids, and faces with two equivalent O(2)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 0-60°. In the fourth O site, O(4) is bonded to four equivalent Na(1) and two equivalent W(1) atoms to form distorted ONa4W2 octahedra that share corners with two equivalent O(3)Na4W2 octahedra, corners with six equivalent O(4)Na4W2 octahedra, corners with five equivalent O(1)Na3W2 square pyramids, corners with nine equivalent O(2)Na3W2 square pyramids,  an edgeedge with one O(3)Na4W2 octahedra,  an edgeedge with one O(4)Na4W2 octahedra,  an edgeedge with one O(1)Na3W2 square pyramid,  an edgeedge with one O(2)Na3W2 square pyramid, faces with two equivalent O(3)Na4W2 octahedra, faces with two equivalent O(4)Na4W2 octahedra,  a faceface with one O(2)Na3W2 square pyramid, and faces with three equivalent O(1)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 0-60°.