AgSO3F crystallizes in the monoclinic P2_1 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form distorted AgO5F octahedra that share  a cornercorner with one Ag(2)O6 octahedra, corners with three equivalent S(1)O3F tetrahedra, corners with three equivalent S(2)O3F tetrahedra, and edges with two equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. In the second Ag site, Ag(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form AgO6 octahedra that share  a cornercorner with one Ag(1)O5F octahedra, corners with three equivalent S(1)O3F tetrahedra, corners with three equivalent S(2)O3F tetrahedra, and edges with two equivalent Ag(1)O5F octahedra. The corner-sharing octahedral tilt angles are 57°. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(3), one O(4), one O(6), and one F(2) atom to form SO3F tetrahedra that share corners with three equivalent Ag(1)O5F octahedra and corners with three equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-60°. In the second S site, S(2) is bonded to one O(1), one O(2), one O(5), and one F(1) atom to form SO3F tetrahedra that share corners with three equivalent Ag(1)O5F octahedra and corners with three equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Ag(2) and one S(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one S(2) atom. In the second F site, F(2) is bonded in a single-bond geometry to one Ag(1) and one S(1) atom.
AgSO3F crystallizes in the monoclinic P2_1 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one F(2) atom to form distorted AgO5F octahedra that share  a cornercorner with one Ag(2)O6 octahedra, corners with three equivalent S(1)O3F tetrahedra, corners with three equivalent S(2)O3F tetrahedra, and edges with two equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. The Ag(1)-O(1) bond length is 2.56 Å. The Ag(1)-O(2) bond length is 2.60 Å. The Ag(1)-O(3) bond length is 2.52 Å. The Ag(1)-O(4) bond length is 2.50 Å. The Ag(1)-O(5) bond length is 2.49 Å. The Ag(1)-F(2) bond length is 2.77 Å. In the second Ag site, Ag(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form AgO6 octahedra that share  a cornercorner with one Ag(1)O5F octahedra, corners with three equivalent S(1)O3F tetrahedra, corners with three equivalent S(2)O3F tetrahedra, and edges with two equivalent Ag(1)O5F octahedra. The corner-sharing octahedral tilt angles are 57°. The Ag(2)-O(1) bond length is 2.67 Å. The Ag(2)-O(2) bond length is 2.57 Å. The Ag(2)-O(3) bond length is 2.51 Å. The Ag(2)-O(4) bond length is 2.49 Å. The Ag(2)-O(5) bond length is 2.49 Å. The Ag(2)-O(6) bond length is 2.66 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(3), one O(4), one O(6), and one F(2) atom to form SO3F tetrahedra that share corners with three equivalent Ag(1)O5F octahedra and corners with three equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-60°. The S(1)-O(3) bond length is 1.47 Å. The S(1)-O(4) bond length is 1.46 Å. The S(1)-O(6) bond length is 1.44 Å. The S(1)-F(2) bond length is 1.63 Å. In the second S site, S(2) is bonded to one O(1), one O(2), one O(5), and one F(1) atom to form SO3F tetrahedra that share corners with three equivalent Ag(1)O5F octahedra and corners with three equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. The S(2)-O(1) bond length is 1.46 Å. The S(2)-O(2) bond length is 1.46 Å. The S(2)-O(5) bond length is 1.47 Å. The S(2)-F(1) bond length is 1.61 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Ag(1), one Ag(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Ag(1), one Ag(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Ag(2) and one S(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one S(2) atom. In the second F site, F(2) is bonded in a single-bond geometry to one Ag(1) and one S(1) atom.