Na3WO4F is Ilmenite-derived structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent F(1) atoms to form distorted NaO4F2 pentagonal pyramids that share corners with two equivalent Na(2)O4F2 octahedra, corners with three equivalent Na(1)O4F2 pentagonal pyramids, corners with four equivalent W(1)O4 tetrahedra, edges with two equivalent Na(1)O4F2 pentagonal pyramids, faces with two equivalent Na(2)O4F2 octahedra, and  a faceface with one Na(1)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 71-74°. In the second Na site, Na(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with two equivalent Na(2)O4F2 octahedra, corners with four equivalent Na(1)O4F2 pentagonal pyramids, corners with four equivalent W(1)O4 tetrahedra, and faces with four equivalent Na(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 14°. W(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form WO4 tetrahedra that share corners with four equivalent Na(2)O4F2 octahedra and corners with eight equivalent Na(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 49-66°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one W(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one W(1) atom. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), and one W(1) atom to form ONa3W tetrahedra that share corners with six equivalent F(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 9-66°. F(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form FNa6 octahedra that share corners with six equivalent O(3)Na3W tetrahedra and faces with two equivalent F(1)Na6 octahedra.
Na3WO4F is Ilmenite-derived structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent F(1) atoms to form distorted NaO4F2 pentagonal pyramids that share corners with two equivalent Na(2)O4F2 octahedra, corners with three equivalent Na(1)O4F2 pentagonal pyramids, corners with four equivalent W(1)O4 tetrahedra, edges with two equivalent Na(1)O4F2 pentagonal pyramids, faces with two equivalent Na(2)O4F2 octahedra, and  a faceface with one Na(1)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 71-74°. The Na(1)-O(2) bond length is 2.40 Å. The Na(1)-O(3) bond length is 2.76 Å. There is one shorter (2.38 Å) and one longer (2.50 Å) Na(1)-O(1) bond length. There is one shorter (2.32 Å) and one longer (2.37 Å) Na(1)-F(1) bond length. In the second Na site, Na(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with two equivalent Na(2)O4F2 octahedra, corners with four equivalent Na(1)O4F2 pentagonal pyramids, corners with four equivalent W(1)O4 tetrahedra, and faces with four equivalent Na(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 14°. The Na(2)-O(2) bond length is 2.41 Å. The Na(2)-O(3) bond length is 2.63 Å. Both Na(2)-O(1) bond lengths are 2.42 Å. There is one shorter (2.26 Å) and one longer (2.47 Å) Na(2)-F(1) bond length. W(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form WO4 tetrahedra that share corners with four equivalent Na(2)O4F2 octahedra and corners with eight equivalent Na(1)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 49-66°. The W(1)-O(2) bond length is 1.81 Å. The W(1)-O(3) bond length is 1.83 Å. Both W(1)-O(1) bond lengths are 1.82 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one W(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one W(1) atom. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), and one W(1) atom to form ONa3W tetrahedra that share corners with six equivalent F(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 9-66°. F(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form FNa6 octahedra that share corners with six equivalent O(3)Na3W tetrahedra and faces with two equivalent F(1)Na6 octahedra.