Sb3O7F crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Sb(2)O6F pentagonal bipyramids, and edges with two equivalent Sb(2)O6F pentagonal bipyramids. The corner-sharing octahedra are not tilted. In the second Sb site, Sb(2) is bonded to two equivalent O(3), four equivalent O(1), and one F(1) atom to form SbO6F pentagonal bipyramids that share corners with two equivalent Sb(1)O6 octahedra, corners with three equivalent Sb(2)O6F pentagonal bipyramids,  an edgeedge with one Sb(1)O6 octahedra, and edges with two equivalent Sb(2)O6F pentagonal bipyramids. The corner-sharing octahedral tilt angles are 37°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Sb(1) and two equivalent Sb(2) atoms. In the second O site, O(2) is bonded in a linear geometry to two equivalent Sb(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent Sb(2) atoms. F(1) is bonded in a linear geometry to two equivalent Sb(2) atoms.
Sb3O7F crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Sb(2)O6F pentagonal bipyramids, and edges with two equivalent Sb(2)O6F pentagonal bipyramids. The corner-sharing octahedra are not tilted. Both Sb(1)-O(2) bond lengths are 1.92 Å. All Sb(1)-O(1) bond lengths are 2.03 Å. In the second Sb site, Sb(2) is bonded to two equivalent O(3), four equivalent O(1), and one F(1) atom to form SbO6F pentagonal bipyramids that share corners with two equivalent Sb(1)O6 octahedra, corners with three equivalent Sb(2)O6F pentagonal bipyramids,  an edgeedge with one Sb(1)O6 octahedra, and edges with two equivalent Sb(2)O6F pentagonal bipyramids. The corner-sharing octahedral tilt angles are 37°. Both Sb(2)-O(3) bond lengths are 1.92 Å. There are two shorter (2.08 Å) and two longer (2.13 Å) Sb(2)-O(1) bond lengths. The Sb(2)-F(1) bond length is 2.16 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Sb(1) and two equivalent Sb(2) atoms. In the second O site, O(2) is bonded in a linear geometry to two equivalent Sb(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent Sb(2) atoms. F(1) is bonded in a linear geometry to two equivalent Sb(2) atoms.