Ca2AlH8S2Cl(O6F)2 crystallizes in the tetragonal I4/m space group. Ca(1) is bonded to four equivalent O(1), one Cl(1), and one F(1) atom to form CaClO4F octahedra that share  a cornercorner with one Ca(1)ClO4F octahedra,  a cornercorner with one Al(1)O4F2 octahedra, and corners with four equivalent S(1)O4 tetrahedra. The corner-sharing octahedra are not tilted. Al(1) is bonded to four equivalent O(2) and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent Ca(1)ClO4F octahedra. The corner-sharing octahedra are not tilted. H(1) is bonded in a single-bond geometry to one O(2) atom. S(1) is bonded to four equivalent O(1) atoms to form SO4 tetrahedra that share corners with four equivalent Ca(1)ClO4F octahedra. The corner-sharing octahedral tilt angles are 50°. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted trigonal planar geometry to one Al(1) and two equivalent H(1) atoms. In the second O site, O(1) is bonded in a 2-coordinate geometry to one Ca(1) and one S(1) atom. Cl(1) is bonded in a linear geometry to two equivalent Ca(1) atoms. F(1) is bonded in a linear geometry to one Ca(1) and one Al(1) atom.
Ca2AlH8S2Cl(O6F)2 crystallizes in the tetragonal I4/m space group. Ca(1) is bonded to four equivalent O(1), one Cl(1), and one F(1) atom to form CaClO4F octahedra that share  a cornercorner with one Ca(1)ClO4F octahedra,  a cornercorner with one Al(1)O4F2 octahedra, and corners with four equivalent S(1)O4 tetrahedra. The corner-sharing octahedra are not tilted. All Ca(1)-O(1) bond lengths are 2.40 Å. The Ca(1)-Cl(1) bond length is 2.61 Å. The Ca(1)-F(1) bond length is 2.22 Å. Al(1) is bonded to four equivalent O(2) and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent Ca(1)ClO4F octahedra. The corner-sharing octahedra are not tilted. All Al(1)-O(2) bond lengths are 1.94 Å. Both Al(1)-F(1) bond lengths are 1.77 Å. H(1) is bonded in a single-bond geometry to one O(2) atom. The H(1)-O(2) bond length is 0.99 Å. S(1) is bonded to four equivalent O(1) atoms to form SO4 tetrahedra that share corners with four equivalent Ca(1)ClO4F octahedra. The corner-sharing octahedral tilt angles are 50°. All S(1)-O(1) bond lengths are 1.49 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted trigonal planar geometry to one Al(1) and two equivalent H(1) atoms. In the second O site, O(1) is bonded in a 2-coordinate geometry to one Ca(1) and one S(1) atom. Cl(1) is bonded in a linear geometry to two equivalent Ca(1) atoms. F(1) is bonded in a linear geometry to one Ca(1) and one Al(1) atom.