Na4(WO3)5 crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(4), one O(6), two equivalent O(1), two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms to form NaO12 cuboctahedra that share corners with five equivalent Na(1)O12 cuboctahedra, corners with five equivalent Na(2)O12 cuboctahedra,  a faceface with one Na(1)O12 cuboctahedra, faces with three equivalent Na(2)O12 cuboctahedra, faces with two equivalent W(3)O6 octahedra, faces with three equivalent W(1)O6 octahedra, and faces with three equivalent W(2)O6 octahedra. In the second Na site, Na(2) is bonded to one O(5), two equivalent O(1), two equivalent O(3), three equivalent O(4), and four equivalent O(2) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(2)O12 cuboctahedra, corners with five equivalent Na(1)O12 cuboctahedra, faces with two equivalent Na(2)O12 cuboctahedra, faces with three equivalent Na(1)O12 cuboctahedra,  a faceface with one W(3)O6 octahedra, faces with three equivalent W(2)O6 octahedra, and faces with four equivalent W(1)O6 octahedra. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form WO6 octahedra that share  a cornercorner with one W(3)O6 octahedra, corners with two equivalent W(1)O6 octahedra, corners with three equivalent W(2)O6 octahedra, faces with three equivalent Na(1)O12 cuboctahedra, and faces with four equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second W site, W(2) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form WO6 octahedra that share  a cornercorner with one W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with three equivalent W(1)O6 octahedra, faces with three equivalent Na(1)O12 cuboctahedra, and faces with three equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third W site, W(3) is bonded to two equivalent O(5) and four equivalent O(3) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, faces with two equivalent Na(2)O12 cuboctahedra, and faces with four equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent W(1) atoms to form distorted ONa4W2 octahedra that share corners with four equivalent O(4)Na4W2 octahedra, corners with two equivalent O(5)Na3W2 square pyramids, corners with six equivalent O(2)Na3W2 square pyramids, corners with eight equivalent O(3)Na3W2 square pyramids, edges with two equivalent O(2)Na3W2 square pyramids, edges with two equivalent O(3)Na3W2 square pyramids, faces with two equivalent O(1)Na4W2 octahedra, faces with two equivalent O(4)Na4W2 octahedra, faces with two equivalent O(2)Na3W2 square pyramids, and faces with two equivalent O(5)Na3W2 square pyramids. The corner-sharing octahedral tilt angles are 61°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), one W(1), and one W(2) atom to form distorted ONa3W2 square pyramids that share corners with three equivalent O(1)Na4W2 octahedra, corners with three equivalent O(4)Na4W2 octahedra, corners with two equivalent O(2)Na3W2 square pyramids, corners with three equivalent O(5)Na3W2 square pyramids, corners with eight equivalent O(3)Na3W2 square pyramids,  an edgeedge with one O(1)Na4W2 octahedra,  an edgeedge with one O(3)Na3W2 square pyramid,  an edgeedge with one O(5)Na3W2 square pyramid, edges with two equivalent O(2)Na3W2 square pyramids,  a faceface with one O(1)Na4W2 octahedra, faces with two equivalent O(4)Na4W2 octahedra, and  a faceface with one O(2)Na3W2 square pyramid. The corner-sharing octahedral tilt angles range from 1-61°. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), one W(2), and one W(3) atom to form distorted ONa3W2 square pyramids that share corners with three equivalent O(4)Na4W2 octahedra, corners with four equivalent O(1)Na4W2 octahedra,  a cornercorner with one O(3)Na3W2 square pyramid, corners with two equivalent O(5)Na3W2 square pyramids, corners with eight equivalent O(2)Na3W2 square pyramids,  an edgeedge with one O(1)Na4W2 octahedra,  an edgeedge with one O(2)Na3W2 square pyramid,  an edgeedge with one O(5)Na3W2 square pyramid, edges with two equivalent O(3)Na3W2 square pyramids,  a faceface with one O(4)Na4W2 octahedra,  a faceface with one O(5)Na3W2 square pyramid, and faces with two equivalent O(3)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 1-61°. In the fourth O site, O(4) is bonded to one Na(1), three equivalent Na(2), one W(1), and one W(2) atom to form distorted ONa4W2 octahedra that share corners with two equivalent O(4)Na4W2 octahedra, corners with four equivalent O(1)Na4W2 octahedra, corners with two equivalent O(5)Na3W2 square pyramids, corners with six equivalent O(2)Na3W2 square pyramids, corners with six equivalent O(3)Na3W2 square pyramids, edges with two equivalent O(4)Na4W2 octahedra, edges with two equivalent O(5)Na3W2 square pyramids, faces with two equivalent O(1)Na4W2 octahedra, faces with two equivalent O(3)Na3W2 square pyramids, and faces with four equivalent O(2)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 1-61°. In the fifth O site, O(5) is bonded to one Na(2), two equivalent Na(1), one W(1), and one W(3) atom to form distorted ONa3W2 square pyramids that share corners with two equivalent O(1)Na4W2 octahedra, corners with two equivalent O(4)Na4W2 octahedra, corners with three equivalent O(5)Na3W2 square pyramids, corners with four equivalent O(3)Na3W2 square pyramids, corners with six equivalent O(2)Na3W2 square pyramids, edges with two equivalent O(4)Na4W2 octahedra, edges with two equivalent O(2)Na3W2 square pyramids, edges with two equivalent O(3)Na3W2 square pyramids, faces with two equivalent O(1)Na4W2 octahedra, and faces with two equivalent O(3)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 1-61°. In the sixth O site, O(6) is bonded in a distorted square co-planar geometry to two equivalent Na(1) and two equivalent W(2) atoms.
Na4(WO3)5 crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(4), one O(6), two equivalent O(1), two equivalent O(2), two equivalent O(5), and four equivalent O(3) atoms to form NaO12 cuboctahedra that share corners with five equivalent Na(1)O12 cuboctahedra, corners with five equivalent Na(2)O12 cuboctahedra,  a faceface with one Na(1)O12 cuboctahedra, faces with three equivalent Na(2)O12 cuboctahedra, faces with two equivalent W(3)O6 octahedra, faces with three equivalent W(1)O6 octahedra, and faces with three equivalent W(2)O6 octahedra. The Na(1)-O(4) bond length is 2.75 Å. The Na(1)-O(6) bond length is 2.72 Å. Both Na(1)-O(1) bond lengths are 2.75 Å. Both Na(1)-O(2) bond lengths are 2.74 Å. Both Na(1)-O(5) bond lengths are 2.73 Å. There are two shorter (2.70 Å) and two longer (2.72 Å) Na(1)-O(3) bond lengths. In the second Na site, Na(2) is bonded to one O(5), two equivalent O(1), two equivalent O(3), three equivalent O(4), and four equivalent O(2) atoms to form NaO12 cuboctahedra that share corners with four equivalent Na(2)O12 cuboctahedra, corners with five equivalent Na(1)O12 cuboctahedra, faces with two equivalent Na(2)O12 cuboctahedra, faces with three equivalent Na(1)O12 cuboctahedra,  a faceface with one W(3)O6 octahedra, faces with three equivalent W(2)O6 octahedra, and faces with four equivalent W(1)O6 octahedra. The Na(2)-O(5) bond length is 2.71 Å. Both Na(2)-O(1) bond lengths are 2.75 Å. Both Na(2)-O(3) bond lengths are 2.72 Å. There are two shorter (2.73 Å) and one longer (2.74 Å) Na(2)-O(4) bond length. There are two shorter (2.72 Å) and two longer (2.73 Å) Na(2)-O(2) bond lengths. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form WO6 octahedra that share  a cornercorner with one W(3)O6 octahedra, corners with two equivalent W(1)O6 octahedra, corners with three equivalent W(2)O6 octahedra, faces with three equivalent Na(1)O12 cuboctahedra, and faces with four equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. The W(1)-O(4) bond length is 1.94 Å. The W(1)-O(5) bond length is 1.92 Å. Both W(1)-O(1) bond lengths are 1.95 Å. Both W(1)-O(2) bond lengths are 1.92 Å. In the second W site, W(2) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form WO6 octahedra that share  a cornercorner with one W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, corners with three equivalent W(1)O6 octahedra, faces with three equivalent Na(1)O12 cuboctahedra, and faces with three equivalent Na(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. The W(2)-O(4) bond length is 1.96 Å. The W(2)-O(6) bond length is 1.91 Å. Both W(2)-O(2) bond lengths are 1.94 Å. Both W(2)-O(3) bond lengths are 1.93 Å. In the third W site, W(3) is bonded to two equivalent O(5) and four equivalent O(3) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, faces with two equivalent Na(2)O12 cuboctahedra, and faces with four equivalent Na(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. Both W(3)-O(5) bond lengths are 1.94 Å. All W(3)-O(3) bond lengths are 1.93 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent W(1) atoms to form distorted ONa4W2 octahedra that share corners with four equivalent O(4)Na4W2 octahedra, corners with two equivalent O(5)Na3W2 square pyramids, corners with six equivalent O(2)Na3W2 square pyramids, corners with eight equivalent O(3)Na3W2 square pyramids, edges with two equivalent O(2)Na3W2 square pyramids, edges with two equivalent O(3)Na3W2 square pyramids, faces with two equivalent O(1)Na4W2 octahedra, faces with two equivalent O(4)Na4W2 octahedra, faces with two equivalent O(2)Na3W2 square pyramids, and faces with two equivalent O(5)Na3W2 square pyramids. The corner-sharing octahedral tilt angles are 61°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), one W(1), and one W(2) atom to form distorted ONa3W2 square pyramids that share corners with three equivalent O(1)Na4W2 octahedra, corners with three equivalent O(4)Na4W2 octahedra, corners with two equivalent O(2)Na3W2 square pyramids, corners with three equivalent O(5)Na3W2 square pyramids, corners with eight equivalent O(3)Na3W2 square pyramids,  an edgeedge with one O(1)Na4W2 octahedra,  an edgeedge with one O(3)Na3W2 square pyramid,  an edgeedge with one O(5)Na3W2 square pyramid, edges with two equivalent O(2)Na3W2 square pyramids,  a faceface with one O(1)Na4W2 octahedra, faces with two equivalent O(4)Na4W2 octahedra, and  a faceface with one O(2)Na3W2 square pyramid. The corner-sharing octahedral tilt angles range from 1-61°. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), one W(2), and one W(3) atom to form distorted ONa3W2 square pyramids that share corners with three equivalent O(4)Na4W2 octahedra, corners with four equivalent O(1)Na4W2 octahedra,  a cornercorner with one O(3)Na3W2 square pyramid, corners with two equivalent O(5)Na3W2 square pyramids, corners with eight equivalent O(2)Na3W2 square pyramids,  an edgeedge with one O(1)Na4W2 octahedra,  an edgeedge with one O(2)Na3W2 square pyramid,  an edgeedge with one O(5)Na3W2 square pyramid, edges with two equivalent O(3)Na3W2 square pyramids,  a faceface with one O(4)Na4W2 octahedra,  a faceface with one O(5)Na3W2 square pyramid, and faces with two equivalent O(3)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 1-61°. In the fourth O site, O(4) is bonded to one Na(1), three equivalent Na(2), one W(1), and one W(2) atom to form distorted ONa4W2 octahedra that share corners with two equivalent O(4)Na4W2 octahedra, corners with four equivalent O(1)Na4W2 octahedra, corners with two equivalent O(5)Na3W2 square pyramids, corners with six equivalent O(2)Na3W2 square pyramids, corners with six equivalent O(3)Na3W2 square pyramids, edges with two equivalent O(4)Na4W2 octahedra, edges with two equivalent O(5)Na3W2 square pyramids, faces with two equivalent O(1)Na4W2 octahedra, faces with two equivalent O(3)Na3W2 square pyramids, and faces with four equivalent O(2)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 1-61°. In the fifth O site, O(5) is bonded to one Na(2), two equivalent Na(1), one W(1), and one W(3) atom to form distorted ONa3W2 square pyramids that share corners with two equivalent O(1)Na4W2 octahedra, corners with two equivalent O(4)Na4W2 octahedra, corners with three equivalent O(5)Na3W2 square pyramids, corners with four equivalent O(3)Na3W2 square pyramids, corners with six equivalent O(2)Na3W2 square pyramids, edges with two equivalent O(4)Na4W2 octahedra, edges with two equivalent O(2)Na3W2 square pyramids, edges with two equivalent O(3)Na3W2 square pyramids, faces with two equivalent O(1)Na4W2 octahedra, and faces with two equivalent O(3)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 1-61°. In the sixth O site, O(6) is bonded in a distorted square co-planar geometry to two equivalent Na(1) and two equivalent W(2) atoms.