Al2P2O8F crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Al(1)O4F2 octahedra. The Al(1)-O(1) bond length is 1.81 Å. The Al(1)-O(2) bond length is 1.88 Å. The Al(1)-O(4) bond length is 1.95 Å. The Al(1)-O(5) bond length is 1.94 Å. There is one shorter (1.87 Å) and one longer (1.95 Å) Al(1)-F(1) bond length. In the second Al site, Al(2) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form AlO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Al(2)-O(3) bond length is 1.72 Å. The Al(2)-O(6) bond length is 1.69 Å. The Al(2)-O(7) bond length is 1.78 Å. The Al(2)-O(8) bond length is 1.73 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra and corners with two equivalent Al(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-56°. The P(1)-O(4) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.48 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra and corners with two equivalent Al(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-34°. The P(2)-O(1) bond length is 1.46 Å. The P(2)-O(2) bond length is 1.48 Å. The P(2)-O(3) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Al(1) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Al(1) and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Al(2) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Al(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Al(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Al(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Al(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Al(2) and one P(2) atom. F(1) is bonded in a water-like geometry to two equivalent Al(1) atoms. Linkers: 8 [O]P([O])([O])=O. Metal clusters: 8 [Al]. The MOF has largest included sphere 4.09 A, density 1.84 g/cm3, surface area 2569.76 m2/g, accessible volume 0.26 cm3/g