Na3MoO3F3 is Ilmenite-derived structured and crystallizes in the trigonal R3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 pentagonal pyramids that share corners with three equivalent Mo(1)O3F3 octahedra, corners with six equivalent Na(3)O3F3 pentagonal pyramids, edges with three equivalent Na(2)O3F3 octahedra, and  a faceface with one Mo(1)O3F3 octahedra. The corner-sharing octahedral tilt angles are 59°. In the second Na site, Na(2) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form NaO3F3 octahedra that share corners with six equivalent Mo(1)O3F3 octahedra, corners with three equivalent Na(3)O3F3 pentagonal pyramids, edges with three equivalent Na(1)O3F3 pentagonal pyramids, and  a faceface with one Na(3)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 38-39°. In the third Na site, Na(3) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 pentagonal pyramids that share corners with three equivalent Na(2)O3F3 octahedra, corners with six equivalent Na(1)O3F3 pentagonal pyramids, edges with three equivalent Mo(1)O3F3 octahedra, and  a faceface with one Na(2)O3F3 octahedra. The corner-sharing octahedral tilt angles are 72°. Mo(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted MoO3F3 octahedra that share corners with six equivalent Na(2)O3F3 octahedra, corners with three equivalent Na(1)O3F3 pentagonal pyramids, edges with three equivalent Na(3)O3F3 pentagonal pyramids, and  a faceface with one Na(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 38-39°. O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one Mo(1) atom. F(1) is bonded to one Na(1), one Na(2), one Na(3), and one Mo(1) atom to form a mixture of distorted corner and edge-sharing FNa3Mo trigonal pyramids.
Na3MoO3F3 is Ilmenite-derived structured and crystallizes in the trigonal R3 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 pentagonal pyramids that share corners with three equivalent Mo(1)O3F3 octahedra, corners with six equivalent Na(3)O3F3 pentagonal pyramids, edges with three equivalent Na(2)O3F3 octahedra, and  a faceface with one Mo(1)O3F3 octahedra. The corner-sharing octahedral tilt angles are 59°. All Na(1)-O(1) bond lengths are 2.33 Å. All Na(1)-F(1) bond lengths are 2.32 Å. In the second Na site, Na(2) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form NaO3F3 octahedra that share corners with six equivalent Mo(1)O3F3 octahedra, corners with three equivalent Na(3)O3F3 pentagonal pyramids, edges with three equivalent Na(1)O3F3 pentagonal pyramids, and  a faceface with one Na(3)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 38-39°. All Na(2)-O(1) bond lengths are 2.41 Å. All Na(2)-F(1) bond lengths are 2.23 Å. In the third Na site, Na(3) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted NaO3F3 pentagonal pyramids that share corners with three equivalent Na(2)O3F3 octahedra, corners with six equivalent Na(1)O3F3 pentagonal pyramids, edges with three equivalent Mo(1)O3F3 octahedra, and  a faceface with one Na(2)O3F3 octahedra. The corner-sharing octahedral tilt angles are 72°. All Na(3)-O(1) bond lengths are 2.45 Å. All Na(3)-F(1) bond lengths are 2.25 Å. Mo(1) is bonded to three equivalent O(1) and three equivalent F(1) atoms to form distorted MoO3F3 octahedra that share corners with six equivalent Na(2)O3F3 octahedra, corners with three equivalent Na(1)O3F3 pentagonal pyramids, edges with three equivalent Na(3)O3F3 pentagonal pyramids, and  a faceface with one Na(1)O3F3 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 38-39°. All Mo(1)-O(1) bond lengths are 1.75 Å. All Mo(1)-F(1) bond lengths are 2.12 Å. O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one Mo(1) atom. F(1) is bonded to one Na(1), one Na(2), one Na(3), and one Mo(1) atom to form a mixture of distorted corner and edge-sharing FNa3Mo trigonal pyramids.