Na2W4O13 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(7), two equivalent O(6), and three equivalent O(5) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(4), one O(5), one O(7), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 0-21°. In the second W site, W(2) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 8-21°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one W(1) and two equivalent W(2) atoms. In the second O site, O(2) is bonded in a linear geometry to two equivalent W(2) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent W(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent W(1) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one W(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one W(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Na(1), one W(1), and one W(2) atom.
Na2W4O13 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 6-coordinate geometry to one O(7), two equivalent O(6), and three equivalent O(5) atoms. The Na(1)-O(7) bond length is 2.38 Å. There is one shorter (2.46 Å) and one longer (2.49 Å) Na(1)-O(6) bond length. There are a spread of Na(1)-O(5) bond distances ranging from 2.50-2.82 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(4), one O(5), one O(7), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 0-21°. The W(1)-O(1) bond length is 2.18 Å. The W(1)-O(4) bond length is 1.94 Å. The W(1)-O(5) bond length is 1.79 Å. The W(1)-O(7) bond length is 1.99 Å. There is one shorter (1.91 Å) and one longer (1.95 Å) W(1)-O(3) bond length. In the second W site, W(2) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 8-21°. The W(2)-O(6) bond length is 1.78 Å. The W(2)-O(7) bond length is 1.96 Å. There is one shorter (1.93 Å) and one longer (2.30 Å) W(2)-O(1) bond length. There is one shorter (1.91 Å) and one longer (1.96 Å) W(2)-O(2) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one W(1) and two equivalent W(2) atoms. In the second O site, O(2) is bonded in a linear geometry to two equivalent W(2) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent W(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent W(1) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one W(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one W(2) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Na(1), one W(1), and one W(2) atom.