Na3(W2O3)2 crystallizes in the orthorhombic Imm2 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(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. W(1) is bonded in a T-shaped geometry to one O(1), one O(2), and one O(3) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), and two equivalent W(1) atoms to form a mixture of distorted corner and edge-sharing ONa3W2 trigonal bipyramids. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), and two equivalent W(1) atoms to form a mixture of distorted face, corner, and edge-sharing ONa3W2 square pyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and two equivalent W(1) atoms to form a mixture of face, corner, and edge-sharing ONa3W2 square pyramids.
Na3(W2O3)2 crystallizes in the orthorhombic Imm2 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(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(1)-O(1) bond lengths are 2.77 Å. Both Na(1)-O(2) bond lengths are 2.83 Å. Both Na(1)-O(3) bond lengths are 2.44 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(2)-O(1) bond lengths are 2.59 Å. Both Na(2)-O(2) bond lengths are 2.63 Å. Both Na(2)-O(3) bond lengths are 2.52 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(3)-O(1) bond lengths are 2.62 Å. Both Na(3)-O(2) bond lengths are 2.59 Å. Both Na(3)-O(3) bond lengths are 2.61 Å. W(1) is bonded in a T-shaped geometry to one O(1), one O(2), and one O(3) atom. The W(1)-O(1) bond length is 1.98 Å. The W(1)-O(2) bond length is 1.97 Å. The W(1)-O(3) bond length is 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), and two equivalent W(1) atoms to form a mixture of distorted corner and edge-sharing ONa3W2 trigonal bipyramids. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), and two equivalent W(1) atoms to form a mixture of distorted face, corner, and edge-sharing ONa3W2 square pyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and two equivalent W(1) atoms to form a mixture of face, corner, and edge-sharing ONa3W2 square pyramids.