AlC2PO3F crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(1) atoms to form AlO4F2 octahedra that share corners with four equivalent P(1)CO3 tetrahedra. Both Al(1)-O(1) bond lengths are 1.86 Å. Both Al(1)-O(3) bond lengths are 1.84 Å. Both Al(1)-F(1) bond lengths are 1.83 Å. In the second Al site, Al(2) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent F(1) atoms. Both Al(2)-O(2) bond lengths are 1.86 Å. Both Al(2)-F(1) bond lengths are 1.82 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a bent 120 degrees geometry to one C(1) and one C(2) atom. The C(1)-C(1) bond length is 1.56 Å. The C(1)-C(2) bond length is 1.52 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(1) and one P(1) atom. The C(2)-P(1) bond length is 1.77 Å. P(1) is bonded to one C(2), one O(1), one O(2), and one O(3) atom to form PCO3 tetrahedra that share corners with two equivalent Al(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-45°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.55 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 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(2) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Al(1) and one P(1) atom. F(1) is bonded in a bent 150 degrees geometry to one Al(1) and one Al(2) atom. Linkers: 2 [O]P([O])(=O)[C]/[C]=[C]/[C]P([O])([O])=O. Metal clusters: 4 [Al]. The MOF has largest included sphere 4.12 A, density 1.53 g/cm3, surface area 3307.89 m2/g, accessible volume 0.32 cm3/g