Na6W10O33 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted see-saw-like geometry to one O(1), one O(2), one O(3), and one O(6) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(16), one O(6), and one O(9) atom. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(12), one O(14), one O(15), one O(16), one O(17), and one O(8) atom. There are five inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. In the second W site, W(2) is bonded to one O(10), one O(14), one O(15), one O(2), one O(4), and one O(9) atom to form distorted corner-sharing WO6 octahedra. The corner-sharing octahedra are not tilted. In the third W site, W(3) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(5), one O(7), and two equivalent O(3) atoms. In the fourth W site, W(4) is bonded in a 5-coordinate geometry to one O(16), one O(2), one O(6), and two equivalent O(14) atoms. In the fifth W site, W(5) is bonded in a 6-coordinate geometry to one O(13), one O(17), one O(5), one O(7), and two equivalent O(1) atoms. There are seventeen inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one W(1), and two equivalent W(5) atoms to form a mixture of distorted edge and corner-sharing ONaW3 tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Na(1), one W(2), and one W(4) atom. In the third O site, O(3) is bonded to one Na(1), one W(1), and two equivalent W(3) atoms to form a mixture of edge and corner-sharing ONaW3 tetrahedra. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one W(1) and one W(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one W(1), one W(3), and one W(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one W(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one W(1), one W(3), and one W(5) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Na(3) and one W(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one W(2) atom. In the tenth O site, O(10) is bonded in a linear geometry to two equivalent W(2) atoms. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Na(2) and one W(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Na(3) and one W(3) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one W(5) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one W(2), and two equivalent W(4) atoms. In the fifteenth O site, O(15) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Na(3), and one W(2) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Na(2), one Na(3), and one W(4) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one W(5) atom.
Na6W10O33 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted see-saw-like geometry to one O(1), one O(2), one O(3), and one O(6) atom. The Na(1)-O(1) bond length is 2.63 Å. The Na(1)-O(2) bond length is 2.46 Å. The Na(1)-O(3) bond length is 2.70 Å. The Na(1)-O(6) bond length is 2.58 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(15), one O(16), one O(6), and one O(9) atom. The Na(2)-O(11) bond length is 2.30 Å. The Na(2)-O(13) bond length is 2.39 Å. The Na(2)-O(15) bond length is 2.44 Å. The Na(2)-O(16) bond length is 2.39 Å. The Na(2)-O(6) bond length is 2.76 Å. The Na(2)-O(9) bond length is 2.35 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(12), one O(14), one O(15), one O(16), one O(17), and one O(8) atom. The Na(3)-O(12) bond length is 2.29 Å. The Na(3)-O(14) bond length is 2.93 Å. The Na(3)-O(15) bond length is 2.64 Å. The Na(3)-O(16) bond length is 2.47 Å. The Na(3)-O(17) bond length is 2.46 Å. The Na(3)-O(8) bond length is 2.57 Å. There are five inequivalent W sites. In the first W site, W(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom. The W(1)-O(1) bond length is 1.98 Å. The W(1)-O(3) bond length is 1.97 Å. The W(1)-O(4) bond length is 1.81 Å. The W(1)-O(5) bond length is 2.25 Å. The W(1)-O(7) bond length is 2.24 Å. The W(1)-O(8) bond length is 1.77 Å. In the second W site, W(2) is bonded to one O(10), one O(14), one O(15), one O(2), one O(4), and one O(9) atom to form distorted corner-sharing WO6 octahedra. The corner-sharing octahedra are not tilted. The W(2)-O(10) bond length is 1.93 Å. The W(2)-O(14) bond length is 2.25 Å. The W(2)-O(15) bond length is 1.78 Å. The W(2)-O(2) bond length is 2.01 Å. The W(2)-O(4) bond length is 2.31 Å. The W(2)-O(9) bond length is 1.76 Å. In the third W site, W(3) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(5), one O(7), and two equivalent O(3) atoms. The W(3)-O(11) bond length is 1.76 Å. The W(3)-O(12) bond length is 1.75 Å. The W(3)-O(5) bond length is 2.01 Å. The W(3)-O(7) bond length is 2.00 Å. There is one shorter (2.24 Å) and one longer (2.35 Å) W(3)-O(3) bond length. In the fourth W site, W(4) is bonded in a 5-coordinate geometry to one O(16), one O(2), one O(6), and two equivalent O(14) atoms. The W(4)-O(16) bond length is 1.77 Å. The W(4)-O(2) bond length is 1.96 Å. The W(4)-O(6) bond length is 1.77 Å. There is one shorter (1.97 Å) and one longer (2.16 Å) W(4)-O(14) bond length. In the fifth W site, W(5) is bonded in a 6-coordinate geometry to one O(13), one O(17), one O(5), one O(7), and two equivalent O(1) atoms. The W(5)-O(13) bond length is 1.76 Å. The W(5)-O(17) bond length is 1.76 Å. The W(5)-O(5) bond length is 2.00 Å. The W(5)-O(7) bond length is 2.01 Å. There is one shorter (2.23 Å) and one longer (2.34 Å) W(5)-O(1) bond length. There are seventeen inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one W(1), and two equivalent W(5) atoms to form a mixture of distorted edge and corner-sharing ONaW3 tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Na(1), one W(2), and one W(4) atom. In the third O site, O(3) is bonded to one Na(1), one W(1), and two equivalent W(3) atoms to form a mixture of edge and corner-sharing ONaW3 tetrahedra. In the fourth O site, O(4) is bonded in a 1-coordinate geometry to one W(1) and one W(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one W(1), one W(3), and one W(5) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one W(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one W(1), one W(3), and one W(5) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Na(3) and one W(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one W(2) atom. In the tenth O site, O(10) is bonded in a linear geometry to two equivalent W(2) atoms. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Na(2) and one W(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Na(3) and one W(3) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one W(5) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one W(2), and two equivalent W(4) atoms. In the fifteenth O site, O(15) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Na(3), and one W(2) atom. In the sixteenth O site, O(16) is bonded in a distorted T-shaped geometry to one Na(2), one Na(3), and one W(4) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one W(5) atom.