Ba4OF6 crystallizes in the tetragonal P4_2/nmc space group. Ba(1) is bonded to one O(1), two equivalent F(2), and four equivalent F(1) atoms to form a mixture of distorted edge and corner-sharing BaOF6 pentagonal bipyramids. O(1) is bonded to four equivalent Ba(1) atoms to form OBa4 tetrahedra that share corners with eight equivalent F(1)Ba4 tetrahedra, corners with eight equivalent F(2)Ba4 tetrahedra, and edges with four equivalent F(1)Ba4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Ba(1) atoms to form FBa4 tetrahedra that share corners with two equivalent O(1)Ba4 tetrahedra, corners with four equivalent F(2)Ba4 tetrahedra, corners with eight equivalent F(1)Ba4 tetrahedra,  an edgeedge with one O(1)Ba4 tetrahedra, edges with two equivalent F(1)Ba4 tetrahedra, and edges with two equivalent F(2)Ba4 tetrahedra. In the second F site, F(2) is bonded to four equivalent Ba(1) atoms to form FBa4 tetrahedra that share corners with four equivalent O(1)Ba4 tetrahedra, corners with eight equivalent F(1)Ba4 tetrahedra, edges with two equivalent F(2)Ba4 tetrahedra, and edges with four equivalent F(1)Ba4 tetrahedra.
Ba4OF6 crystallizes in the tetragonal P4_2/nmc space group. Ba(1) is bonded to one O(1), two equivalent F(2), and four equivalent F(1) atoms to form a mixture of distorted edge and corner-sharing BaOF6 pentagonal bipyramids. The Ba(1)-O(1) bond length is 2.57 Å. There is one shorter (2.63 Å) and one longer (2.70 Å) Ba(1)-F(2) bond length. There are two shorter (2.69 Å) and two longer (2.76 Å) Ba(1)-F(1) bond lengths. O(1) is bonded to four equivalent Ba(1) atoms to form OBa4 tetrahedra that share corners with eight equivalent F(1)Ba4 tetrahedra, corners with eight equivalent F(2)Ba4 tetrahedra, and edges with four equivalent F(1)Ba4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Ba(1) atoms to form FBa4 tetrahedra that share corners with two equivalent O(1)Ba4 tetrahedra, corners with four equivalent F(2)Ba4 tetrahedra, corners with eight equivalent F(1)Ba4 tetrahedra,  an edgeedge with one O(1)Ba4 tetrahedra, edges with two equivalent F(1)Ba4 tetrahedra, and edges with two equivalent F(2)Ba4 tetrahedra. In the second F site, F(2) is bonded to four equivalent Ba(1) atoms to form FBa4 tetrahedra that share corners with four equivalent O(1)Ba4 tetrahedra, corners with eight equivalent F(1)Ba4 tetrahedra, edges with two equivalent F(2)Ba4 tetrahedra, and edges with four equivalent F(1)Ba4 tetrahedra.