Tl2AlOF5 crystallizes in the orthorhombic Cmcm space group. Tl(1) is bonded to one O(1), two equivalent F(1), and two equivalent F(2) atoms to form distorted TlOF4 square pyramids that share corners with four equivalent Al(1)F6 octahedra, corners with two equivalent Tl(1)OF4 square pyramids, and  a faceface with one Tl(1)OF4 square pyramid. The corner-sharing octahedral tilt angles range from 57-65°. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with eight equivalent Tl(1)OF4 square pyramids. The corner-sharing octahedral tilt angles are 16°. O(1) is bonded in a water-like geometry to two equivalent Tl(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Tl(1) and one Al(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to two equivalent Tl(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms.
Tl2AlOF5 crystallizes in the orthorhombic Cmcm space group. Tl(1) is bonded to one O(1), two equivalent F(1), and two equivalent F(2) atoms to form distorted TlOF4 square pyramids that share corners with four equivalent Al(1)F6 octahedra, corners with two equivalent Tl(1)OF4 square pyramids, and  a faceface with one Tl(1)OF4 square pyramid. The corner-sharing octahedral tilt angles range from 57-65°. The Tl(1)-O(1) bond length is 2.23 Å. Both Tl(1)-F(1) bond lengths are 2.62 Å. Both Tl(1)-F(2) bond lengths are 2.72 Å. Al(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form AlF6 octahedra that share corners with two equivalent Al(1)F6 octahedra and corners with eight equivalent Tl(1)OF4 square pyramids. The corner-sharing octahedral tilt angles are 16°. Both Al(1)-F(1) bond lengths are 1.83 Å. Both Al(1)-F(2) bond lengths are 1.81 Å. Both Al(1)-F(3) bond lengths are 1.87 Å. O(1) is bonded in a water-like geometry to two equivalent Tl(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent Tl(1) and one Al(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to two equivalent Tl(1) and one Al(1) atom. In the third F site, F(3) is bonded in a linear geometry to two equivalent Al(1) atoms.