Al2PH2(O3F)2 crystallizes in the trigonal P3_121 space group. Al(1) is bonded to one O(1), one O(2), two equivalent O(3), one F(1), and one F(2) atom to form AlO4F2 octahedra that share corners with two equivalent Al(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 41°. The Al(1)-O(1) bond length is 1.84 Å. The Al(1)-O(2) bond length is 1.86 Å. There is one shorter (1.85 Å) and one longer (1.87 Å) Al(1)-O(3) bond length. The Al(1)-F(1) bond length is 1.90 Å. The Al(1)-F(2) bond length is 1.94 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 40-46°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(2) bond lengths are 1.53 Å. H(1) is bonded in a single-bond geometry to one O(3) atom. The H(1)-O(3) bond length is 0.89 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Al(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Al(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Al(1) and one H(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to two equivalent Al(1) atoms. In the second F site, F(2) is bonded in a water-like geometry to two equivalent Al(1) atoms. Linkers: 3 [O]P([O])([O])=O ,6 [OH]. Metal clusters: 6 [Al]. The MOF has largest included sphere 4.24 A, density 2.08 g/cm3, surface area 2022.54 m2/g, accessible volume 0.16 cm3/g