Cr4OF6 crystallizes in the tetragonal P4_2/nmc space group. Cr(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent F(2), and four equivalent F(1) atoms. O(1) is bonded to four equivalent Cr(1) atoms to form OCr4 tetrahedra that share corners with eight equivalent F(1)Cr4 tetrahedra and edges with four equivalent F(1)Cr4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cr(1) atoms to form FCr4 tetrahedra that share corners with two equivalent O(1)Cr4 tetrahedra, corners with eight equivalent F(1)Cr4 tetrahedra,  an edgeedge with one O(1)Cr4 tetrahedra, and edges with two equivalent F(1)Cr4 tetrahedra. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to four equivalent Cr(1) atoms.
Cr4OF6 crystallizes in the tetragonal P4_2/nmc space group. Cr(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent F(2), and four equivalent F(1) atoms. The Cr(1)-O(1) bond length is 2.05 Å. There is one shorter (2.01 Å) and one longer (2.56 Å) Cr(1)-F(2) bond length. All Cr(1)-F(1) bond lengths are 2.29 Å. O(1) is bonded to four equivalent Cr(1) atoms to form OCr4 tetrahedra that share corners with eight equivalent F(1)Cr4 tetrahedra and edges with four equivalent F(1)Cr4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cr(1) atoms to form FCr4 tetrahedra that share corners with two equivalent O(1)Cr4 tetrahedra, corners with eight equivalent F(1)Cr4 tetrahedra,  an edgeedge with one O(1)Cr4 tetrahedra, and edges with two equivalent F(1)Cr4 tetrahedra. In the second F site, F(2) is bonded in a distorted bent 120 degrees geometry to four equivalent Cr(1) atoms.