NaSO3F crystallizes in the trigonal P-3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to six equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with six equivalent S(1)O3F tetrahedra and faces with two equivalent Na(2)O6 octahedra. In the second Na site, Na(2) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent S(1)O3F tetrahedra and faces with two equivalent Na(1)O6 octahedra. S(1) is bonded to three equivalent O(1) and one F(1) atom to form SO3F tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-56°. O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one S(1) atom. F(1) is bonded in a single-bond geometry to one S(1) atom.
NaSO3F crystallizes in the trigonal P-3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to six equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with six equivalent S(1)O3F tetrahedra and faces with two equivalent Na(2)O6 octahedra. All Na(1)-O(1) bond lengths are 2.50 Å. In the second Na site, Na(2) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share corners with six equivalent S(1)O3F tetrahedra and faces with two equivalent Na(1)O6 octahedra. All Na(2)-O(1) bond lengths are 2.44 Å. S(1) is bonded to three equivalent O(1) and one F(1) atom to form SO3F tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with three equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-56°. All S(1)-O(1) bond lengths are 1.45 Å. The S(1)-F(1) bond length is 1.63 Å. O(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one S(1) atom. F(1) is bonded in a single-bond geometry to one S(1) atom.