Na(WO3)2 crystallizes in the orthorhombic Imm2 space group. Na(1) is bonded to two equivalent O(2), two equivalent O(3), and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with twelve equivalent Na(1)O12 cuboctahedra and faces with eight equivalent W(1)O6 octahedra. W(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form WO6 octahedra that share corners with six equivalent W(1)O6 octahedra and faces with four equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent W(1) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent W(1) atoms. In the third O site, O(3) is bonded in a distorted square co-planar geometry to two equivalent Na(1) and two equivalent W(1) atoms.
Na(WO3)2 crystallizes in the orthorhombic Imm2 space group. Na(1) is bonded to two equivalent O(2), two equivalent O(3), and eight equivalent O(1) atoms to form NaO12 cuboctahedra that share corners with twelve equivalent Na(1)O12 cuboctahedra and faces with eight equivalent W(1)O6 octahedra. Both Na(1)-O(2) bond lengths are 2.77 Å. There is one shorter (2.75 Å) and one longer (2.78 Å) Na(1)-O(3) bond length. There are four shorter (2.75 Å) and four longer (2.78 Å) Na(1)-O(1) bond lengths. W(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form WO6 octahedra that share corners with six equivalent W(1)O6 octahedra and faces with four equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-2°. The W(1)-O(2) bond length is 1.94 Å. The W(1)-O(3) bond length is 1.97 Å. There are two shorter (1.95 Å) and two longer (1.96 Å) W(1)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent W(1) atoms. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent W(1) atoms. In the third O site, O(3) is bonded in a distorted square co-planar geometry to two equivalent Na(1) and two equivalent W(1) atoms.