Cu4OF6 crystallizes in the tetragonal P4_2/nmc space group. Cu(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), and four equivalent F(1) atoms. O(1) is bonded to four equivalent Cu(1) atoms to form OCu4 tetrahedra that share corners with eight equivalent F(1)Cu4 tetrahedra and edges with four equivalent F(1)Cu4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cu(1) atoms to form distorted FCu4 tetrahedra that share corners with two equivalent O(1)Cu4 tetrahedra, corners with eight equivalent F(1)Cu4 tetrahedra,  an edgeedge with one O(1)Cu4 tetrahedra, and edges with two equivalent F(1)Cu4 tetrahedra. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Cu(1) atoms.
Cu4OF6 crystallizes in the tetragonal P4_2/nmc space group. Cu(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), and four equivalent F(1) atoms. The Cu(1)-O(1) bond length is 1.93 Å. The Cu(1)-F(2) bond length is 1.90 Å. There are two shorter (2.18 Å) and two longer (2.22 Å) Cu(1)-F(1) bond lengths. O(1) is bonded to four equivalent Cu(1) atoms to form OCu4 tetrahedra that share corners with eight equivalent F(1)Cu4 tetrahedra and edges with four equivalent F(1)Cu4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cu(1) atoms to form distorted FCu4 tetrahedra that share corners with two equivalent O(1)Cu4 tetrahedra, corners with eight equivalent F(1)Cu4 tetrahedra,  an edgeedge with one O(1)Cu4 tetrahedra, and edges with two equivalent F(1)Cu4 tetrahedra. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Cu(1) atoms.