Na3W2(OCl)4 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 9-coordinate geometry to four equivalent O(1), one Cl(1), two equivalent Cl(3), and two equivalent Cl(4) atoms. In the second Na site, Na(2) is bonded in a 9-coordinate geometry to four equivalent O(1), one Cl(4), two equivalent Cl(1), and two equivalent Cl(2) atoms. In the third Na site, Na(3) is bonded in a 9-coordinate geometry to four equivalent O(1), one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded to four equivalent O(1), one Cl(1), and one Cl(4) atom to form distorted corner-sharing WCl2O4 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second W site, W(2) is bonded to four equivalent O(1), one Cl(2), and one Cl(3) atom to form distorted corner-sharing WCl2O4 octahedra. The corner-sharing octahedral tilt angles are 5°. O(1) is bonded to one Na(1), one Na(2), one Na(3), one W(1), and one W(2) atom to form distorted ONa3W2 square pyramids that share corners with three equivalent Cl(1)Na5W octahedra, corners with two equivalent Cl(2)Na4W square pyramids, corners with three equivalent O(1)Na3W2 square pyramids, edges with three equivalent O(1)Na3W2 square pyramids,  a faceface with one Cl(1)Na5W octahedra,  a faceface with one Cl(2)Na4W square pyramid, and faces with two equivalent O(1)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 45-51°. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(3), and one W(1) atom to form ClNa5W octahedra that share corners with four equivalent Cl(1)Na5W octahedra, corners with twelve equivalent O(1)Na3W2 square pyramids, edges with four equivalent Cl(2)Na4W square pyramids, and faces with four equivalent O(1)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 22-23°. In the second Cl site, Cl(2) is bonded to two equivalent Na(2), two equivalent Na(3), and one W(2) atom to form ClNa4W square pyramids that share corners with four equivalent Cl(2)Na4W square pyramids, corners with eight equivalent O(1)Na3W2 square pyramids, edges with four equivalent Cl(1)Na5W octahedra, and faces with four equivalent O(1)Na3W2 square pyramids. In the third Cl site, Cl(3) is bonded in a square co-planar geometry to one Na(3), two equivalent Na(1), and one W(2) atom. In the fourth Cl site, Cl(4) is bonded in a square co-planar geometry to one Na(2), two equivalent Na(1), and one W(1) atom.
Na3W2(OCl)4 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 9-coordinate geometry to four equivalent O(1), one Cl(1), two equivalent Cl(3), and two equivalent Cl(4) atoms. All Na(1)-O(1) bond lengths are 2.84 Å. The Na(1)-Cl(1) bond length is 3.04 Å. Both Na(1)-Cl(3) bond lengths are 2.85 Å. Both Na(1)-Cl(4) bond lengths are 2.90 Å. In the second Na site, Na(2) is bonded in a 9-coordinate geometry to four equivalent O(1), one Cl(4), two equivalent Cl(1), and two equivalent Cl(2) atoms. All Na(2)-O(1) bond lengths are 2.76 Å. The Na(2)-Cl(4) bond length is 3.05 Å. Both Na(2)-Cl(1) bond lengths are 2.90 Å. Both Na(2)-Cl(2) bond lengths are 2.85 Å. In the third Na site, Na(3) is bonded in a 9-coordinate geometry to four equivalent O(1), one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms. All Na(3)-O(1) bond lengths are 2.75 Å. The Na(3)-Cl(3) bond length is 3.12 Å. Both Na(3)-Cl(1) bond lengths are 2.87 Å. Both Na(3)-Cl(2) bond lengths are 2.90 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to four equivalent O(1), one Cl(1), and one Cl(4) atom to form distorted corner-sharing WCl2O4 octahedra. The corner-sharing octahedral tilt angles are 5°. All W(1)-O(1) bond lengths are 2.04 Å. The W(1)-Cl(1) bond length is 2.56 Å. The W(1)-Cl(4) bond length is 2.45 Å. In the second W site, W(2) is bonded to four equivalent O(1), one Cl(2), and one Cl(3) atom to form distorted corner-sharing WCl2O4 octahedra. The corner-sharing octahedral tilt angles are 5°. All W(2)-O(1) bond lengths are 1.97 Å. The W(2)-Cl(2) bond length is 2.51 Å. The W(2)-Cl(3) bond length is 2.43 Å. O(1) is bonded to one Na(1), one Na(2), one Na(3), one W(1), and one W(2) atom to form distorted ONa3W2 square pyramids that share corners with three equivalent Cl(1)Na5W octahedra, corners with two equivalent Cl(2)Na4W square pyramids, corners with three equivalent O(1)Na3W2 square pyramids, edges with three equivalent O(1)Na3W2 square pyramids,  a faceface with one Cl(1)Na5W octahedra,  a faceface with one Cl(2)Na4W square pyramid, and faces with two equivalent O(1)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 45-51°. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Na(1), two equivalent Na(2), two equivalent Na(3), and one W(1) atom to form ClNa5W octahedra that share corners with four equivalent Cl(1)Na5W octahedra, corners with twelve equivalent O(1)Na3W2 square pyramids, edges with four equivalent Cl(2)Na4W square pyramids, and faces with four equivalent O(1)Na3W2 square pyramids. The corner-sharing octahedral tilt angles range from 22-23°. In the second Cl site, Cl(2) is bonded to two equivalent Na(2), two equivalent Na(3), and one W(2) atom to form ClNa4W square pyramids that share corners with four equivalent Cl(2)Na4W square pyramids, corners with eight equivalent O(1)Na3W2 square pyramids, edges with four equivalent Cl(1)Na5W octahedra, and faces with four equivalent O(1)Na3W2 square pyramids. In the third Cl site, Cl(3) is bonded in a square co-planar geometry to one Na(3), two equivalent Na(1), and one W(2) atom. In the fourth Cl site, Cl(4) is bonded in a square co-planar geometry to one Na(2), two equivalent Na(1), and one W(1) atom.