Na(WO3)9 crystallizes in the trigonal R-3 space group. Na(1) is bonded to six equivalent O(2) and six equivalent O(5) atoms to form NaO12 cuboctahedra that share faces with two equivalent W(3)O6 octahedra and faces with six equivalent W(2)O6 octahedra. There are three inequivalent W sites. In the first W site, W(1) is bonded to six equivalent O(1) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedra are not tilted. In the second W site, W(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with three equivalent W(2)O6 octahedra, and  a faceface with one Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third W site, W(3) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form WO6 octahedra that share corners with six equivalent W(2)O6 octahedra and  a faceface with one Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 1-3°. There are five inequivalent O sites. In the first O site, O(3) is bonded in a linear geometry to two equivalent W(2) atoms. In the second O site, O(4) is bonded in a linear geometry to one W(2) and one W(3) atom. In the third O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1), one W(2), and one W(3) atom. In the fourth O site, O(1) is bonded in a linear geometry to one W(1) and one W(2) atom. In the fifth O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent W(2) atoms.
Na(WO3)9 crystallizes in the trigonal R-3 space group. Na(1) is bonded to six equivalent O(2) and six equivalent O(5) atoms to form NaO12 cuboctahedra that share faces with two equivalent W(3)O6 octahedra and faces with six equivalent W(2)O6 octahedra. All Na(1)-O(2) bond lengths are 2.67 Å. All Na(1)-O(5) bond lengths are 2.66 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded to six equivalent O(1) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedra are not tilted. All W(1)-O(1) bond lengths are 1.90 Å. In the second W site, W(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with three equivalent W(2)O6 octahedra, and  a faceface with one Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. The W(2)-O(1) bond length is 1.89 Å. The W(2)-O(3) bond length is 1.90 Å. The W(2)-O(4) bond length is 1.91 Å. The W(2)-O(5) bond length is 1.91 Å. There is one shorter (1.91 Å) and one longer (1.93 Å) W(2)-O(2) bond length. In the third W site, W(3) is bonded to three equivalent O(4) and three equivalent O(5) atoms to form WO6 octahedra that share corners with six equivalent W(2)O6 octahedra and  a faceface with one Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 1-3°. All W(3)-O(4) bond lengths are 1.89 Å. All W(3)-O(5) bond lengths are 1.93 Å. There are five inequivalent O sites. In the first O site, O(3) is bonded in a linear geometry to two equivalent W(2) atoms. In the second O site, O(4) is bonded in a linear geometry to one W(2) and one W(3) atom. In the third O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1), one W(2), and one W(3) atom. In the fourth O site, O(1) is bonded in a linear geometry to one W(1) and one W(2) atom. In the fifth O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent W(2) atoms.