Fe4OF6 crystallizes in the tetragonal P4_2/nmc space group. Fe(1) is bonded to one O(1), two equivalent F(1), and four equivalent F(2) atoms to form a mixture of distorted corner and edge-sharing FeOF6 pentagonal bipyramids. O(1) is bonded to four equivalent Fe(1) atoms to form OFe4 tetrahedra that share corners with eight equivalent F(1)Fe4 tetrahedra, corners with eight equivalent F(2)Fe4 tetrahedra, and edges with four equivalent F(2)Fe4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Fe(1) atoms to form FFe4 tetrahedra that share corners with four equivalent O(1)Fe4 tetrahedra, corners with eight equivalent F(2)Fe4 tetrahedra, edges with two equivalent F(1)Fe4 tetrahedra, and edges with four equivalent F(2)Fe4 tetrahedra. In the second F site, F(2) is bonded to four equivalent Fe(1) atoms to form distorted FFe4 tetrahedra that share corners with two equivalent O(1)Fe4 tetrahedra, corners with four equivalent F(1)Fe4 tetrahedra, corners with eight equivalent F(2)Fe4 tetrahedra,  an edgeedge with one O(1)Fe4 tetrahedra, edges with two equivalent F(1)Fe4 tetrahedra, and edges with two equivalent F(2)Fe4 tetrahedra.
Fe4OF6 crystallizes in the tetragonal P4_2/nmc space group. Fe(1) is bonded to one O(1), two equivalent F(1), and four equivalent F(2) atoms to form a mixture of distorted corner and edge-sharing FeOF6 pentagonal bipyramids. The Fe(1)-O(1) bond length is 2.06 Å. There is one shorter (2.13 Å) and one longer (2.25 Å) Fe(1)-F(1) bond length. There are two shorter (2.17 Å) and two longer (2.34 Å) Fe(1)-F(2) bond lengths. O(1) is bonded to four equivalent Fe(1) atoms to form OFe4 tetrahedra that share corners with eight equivalent F(1)Fe4 tetrahedra, corners with eight equivalent F(2)Fe4 tetrahedra, and edges with four equivalent F(2)Fe4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Fe(1) atoms to form FFe4 tetrahedra that share corners with four equivalent O(1)Fe4 tetrahedra, corners with eight equivalent F(2)Fe4 tetrahedra, edges with two equivalent F(1)Fe4 tetrahedra, and edges with four equivalent F(2)Fe4 tetrahedra. In the second F site, F(2) is bonded to four equivalent Fe(1) atoms to form distorted FFe4 tetrahedra that share corners with two equivalent O(1)Fe4 tetrahedra, corners with four equivalent F(1)Fe4 tetrahedra, corners with eight equivalent F(2)Fe4 tetrahedra,  an edgeedge with one O(1)Fe4 tetrahedra, edges with two equivalent F(1)Fe4 tetrahedra, and edges with two equivalent F(2)Fe4 tetrahedra.