W5O12F crystallizes in the orthorhombic Pmma space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(3) atoms to form WO6 octahedra that share corners with three equivalent W(1)O6 octahedra,  a cornercorner with one W(2)O7 pentagonal bipyramid, corners with two equivalent W(3)O6F pentagonal bipyramids,  an edgeedge with one W(3)O6F pentagonal bipyramid, and  an edgeedge with one W(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-46°. In the second W site, W(2) is bonded to one O(2), two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form WO7 pentagonal bipyramids that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O7 pentagonal bipyramids, edges with two equivalent W(1)O6 octahedra, and edges with two equivalent W(3)O6F pentagonal bipyramids. The corner-sharing octahedral tilt angles are 34°. In the third W site, W(3) is bonded to one O(1), one O(7), two equivalent O(5), two equivalent O(6), and one F(1) atom to form WO6F pentagonal bipyramids that share corners with two equivalent W(1)O6 octahedra, corners with three equivalent W(3)O6F pentagonal bipyramids,  an edgeedge with one W(1)O6 octahedra,  an edgeedge with one W(3)O6F pentagonal bipyramid, and  an edgeedge with one W(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 40-42°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one W(1), one W(2), and one W(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one W(2) and two equivalent W(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent W(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent W(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent W(3) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one W(1) and two equivalent W(3) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one W(1), one W(2), and one W(3) atom. F(1) is bonded in a linear geometry to two equivalent W(3) atoms.
W5O12F crystallizes in the orthorhombic Pmma space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(2), one O(6), one O(7), and two equivalent O(3) atoms to form WO6 octahedra that share corners with three equivalent W(1)O6 octahedra,  a cornercorner with one W(2)O7 pentagonal bipyramid, corners with two equivalent W(3)O6F pentagonal bipyramids,  an edgeedge with one W(3)O6F pentagonal bipyramid, and  an edgeedge with one W(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-46°. The W(1)-O(1) bond length is 2.07 Å. The W(1)-O(2) bond length is 2.01 Å. The W(1)-O(6) bond length is 2.05 Å. The W(1)-O(7) bond length is 2.05 Å. Both W(1)-O(3) bond lengths are 1.94 Å. In the second W site, W(2) is bonded to one O(2), two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form WO7 pentagonal bipyramids that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O7 pentagonal bipyramids, edges with two equivalent W(1)O6 octahedra, and edges with two equivalent W(3)O6F pentagonal bipyramids. The corner-sharing octahedral tilt angles are 34°. The W(2)-O(2) bond length is 2.12 Å. Both W(2)-O(1) bond lengths are 2.17 Å. Both W(2)-O(4) bond lengths are 1.94 Å. Both W(2)-O(7) bond lengths are 2.10 Å. In the third W site, W(3) is bonded to one O(1), one O(7), two equivalent O(5), two equivalent O(6), and one F(1) atom to form WO6F pentagonal bipyramids that share corners with two equivalent W(1)O6 octahedra, corners with three equivalent W(3)O6F pentagonal bipyramids,  an edgeedge with one W(1)O6 octahedra,  an edgeedge with one W(3)O6F pentagonal bipyramid, and  an edgeedge with one W(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 40-42°. The W(3)-O(1) bond length is 1.97 Å. The W(3)-O(7) bond length is 2.16 Å. Both W(3)-O(5) bond lengths are 1.94 Å. There is one shorter (2.04 Å) and one longer (2.08 Å) W(3)-O(6) bond length. The W(3)-F(1) bond length is 2.25 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one W(1), one W(2), and one W(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one W(2) and two equivalent W(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent W(1) atoms. In the fourth O site, O(4) is bonded in a linear geometry to two equivalent W(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent W(3) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one W(1) and two equivalent W(3) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one W(1), one W(2), and one W(3) atom. F(1) is bonded in a linear geometry to two equivalent W(3) atoms.