Cd4OF6 crystallizes in the tetragonal P4_2/nmc space group. Cd(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 CdOF6 pentagonal bipyramids. O(1) is bonded to four equivalent Cd(1) atoms to form OCd4 tetrahedra that share corners with eight equivalent F(1)Cd4 tetrahedra, corners with eight equivalent F(2)Cd4 tetrahedra, and edges with four equivalent F(2)Cd4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cd(1) atoms to form FCd4 tetrahedra that share corners with four equivalent O(1)Cd4 tetrahedra, corners with eight equivalent F(2)Cd4 tetrahedra, edges with two equivalent F(1)Cd4 tetrahedra, and edges with four equivalent F(2)Cd4 tetrahedra. In the second F site, F(2) is bonded to four equivalent Cd(1) atoms to form distorted FCd4 tetrahedra that share corners with two equivalent O(1)Cd4 tetrahedra, corners with four equivalent F(1)Cd4 tetrahedra, corners with eight equivalent F(2)Cd4 tetrahedra,  an edgeedge with one O(1)Cd4 tetrahedra, edges with two equivalent F(1)Cd4 tetrahedra, and edges with two equivalent F(2)Cd4 tetrahedra.
Cd4OF6 crystallizes in the tetragonal P4_2/nmc space group. Cd(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 CdOF6 pentagonal bipyramids. The Cd(1)-O(1) bond length is 2.18 Å. There is one shorter (2.25 Å) and one longer (2.36 Å) Cd(1)-F(1) bond length. There are two shorter (2.31 Å) and two longer (2.43 Å) Cd(1)-F(2) bond lengths. O(1) is bonded to four equivalent Cd(1) atoms to form OCd4 tetrahedra that share corners with eight equivalent F(1)Cd4 tetrahedra, corners with eight equivalent F(2)Cd4 tetrahedra, and edges with four equivalent F(2)Cd4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cd(1) atoms to form FCd4 tetrahedra that share corners with four equivalent O(1)Cd4 tetrahedra, corners with eight equivalent F(2)Cd4 tetrahedra, edges with two equivalent F(1)Cd4 tetrahedra, and edges with four equivalent F(2)Cd4 tetrahedra. In the second F site, F(2) is bonded to four equivalent Cd(1) atoms to form distorted FCd4 tetrahedra that share corners with two equivalent O(1)Cd4 tetrahedra, corners with four equivalent F(1)Cd4 tetrahedra, corners with eight equivalent F(2)Cd4 tetrahedra,  an edgeedge with one O(1)Cd4 tetrahedra, edges with two equivalent F(1)Cd4 tetrahedra, and edges with two equivalent F(2)Cd4 tetrahedra.