Na3MoO4F 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(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with two equivalent Na(1)O4F2 octahedra, corners with four equivalent Na(2)O4F2 pentagonal pyramids, corners with four equivalent Mo(1)O4 tetrahedra, and faces with four equivalent Na(2)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 12°. In the second Na site, Na(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form distorted NaO4F2 pentagonal pyramids that share corners with two equivalent Na(1)O4F2 octahedra, corners with three equivalent Na(2)O4F2 pentagonal pyramids, corners with four equivalent Mo(1)O4 tetrahedra, edges with two equivalent Na(2)O4F2 pentagonal pyramids, faces with two equivalent Na(1)O4F2 octahedra, and  a faceface with one Na(2)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 71-76°. Mo(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form MoO4 tetrahedra that share corners with four equivalent Na(1)O4F2 octahedra and corners with eight equivalent Na(2)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 49-67°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Mo(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Mo(1) atom. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), and one Mo(1) atom to form ONa3Mo tetrahedra that share corners with six equivalent F(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 11-64°. F(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form FNa6 octahedra that share corners with six equivalent O(3)Na3Mo tetrahedra and faces with two equivalent F(1)Na6 octahedra.
Na3MoO4F 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(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form distorted NaO4F2 octahedra that share corners with two equivalent Na(1)O4F2 octahedra, corners with four equivalent Na(2)O4F2 pentagonal pyramids, corners with four equivalent Mo(1)O4 tetrahedra, and faces with four equivalent Na(2)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 12°. The Na(1)-O(1) bond length is 2.43 Å. The Na(1)-O(3) bond length is 2.60 Å. Both Na(1)-O(2) bond lengths are 2.42 Å. There is one shorter (2.26 Å) and one longer (2.44 Å) Na(1)-F(1) bond length. In the second Na site, Na(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent F(1) atoms to form distorted NaO4F2 pentagonal pyramids that share corners with two equivalent Na(1)O4F2 octahedra, corners with three equivalent Na(2)O4F2 pentagonal pyramids, corners with four equivalent Mo(1)O4 tetrahedra, edges with two equivalent Na(2)O4F2 pentagonal pyramids, faces with two equivalent Na(1)O4F2 octahedra, and  a faceface with one Na(2)O4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 71-76°. The Na(2)-O(1) bond length is 2.40 Å. The Na(2)-O(3) bond length is 2.72 Å. There is one shorter (2.38 Å) and one longer (2.52 Å) Na(2)-O(2) bond length. There is one shorter (2.31 Å) and one longer (2.37 Å) Na(2)-F(1) bond length. Mo(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form MoO4 tetrahedra that share corners with four equivalent Na(1)O4F2 octahedra and corners with eight equivalent Na(2)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 49-67°. The Mo(1)-O(1) bond length is 1.79 Å. The Mo(1)-O(3) bond length is 1.81 Å. Both Mo(1)-O(2) bond lengths are 1.80 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Mo(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one Mo(1) atom. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(2), and one Mo(1) atom to form ONa3Mo tetrahedra that share corners with six equivalent F(1)Na6 octahedra. The corner-sharing octahedral tilt angles range from 11-64°. F(1) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form FNa6 octahedra that share corners with six equivalent O(3)Na3Mo tetrahedra and faces with two equivalent F(1)Na6 octahedra.