Al3P3O12F crystallizes in the triclinic P-1 space group. There are three inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(11), one O(2), and one O(3) atom to form AlO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Al(1)-O(1) bond length is 1.74 Å. The Al(1)-O(11) bond length is 1.72 Å. The Al(1)-O(2) bond length is 1.74 Å. The Al(1)-O(3) bond length is 1.73 Å. In the second Al site, Al(2) is bonded to one O(5), one O(6), one O(8), one O(9), and two equivalent F(1) atoms to form AlO4F2 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Al(2)O4F2 octahedra. The Al(2)-O(5) bond length is 1.82 Å. The Al(2)-O(6) bond length is 1.87 Å. The Al(2)-O(8) bond length is 1.90 Å. The Al(2)-O(9) bond length is 1.82 Å. There is one shorter (1.85 Å) and one longer (1.89 Å) Al(2)-F(1) bond length. In the third Al site, Al(3) is bonded to one O(10), one O(12), one O(4), and one O(7) atom to form AlO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Al(3)-O(10) bond length is 1.74 Å. The Al(3)-O(12) bond length is 1.73 Å. The Al(3)-O(4) bond length is 1.72 Å. The Al(3)-O(7) bond length is 1.73 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Al(2)O4F2 octahedra,  a cornercorner with one Al(3)O4 tetrahedra, and corners with two equivalent Al(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 33°. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.53 Å. The P(1)-O(5) bond length is 1.50 Å. In the second P site, P(2) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Al(2)O4F2 octahedra,  a cornercorner with one Al(1)O4 tetrahedra, and  a cornercorner with one Al(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Al(2)O4F2 octahedra,  a cornercorner with one Al(1)O4 tetrahedra, and corners with two equivalent Al(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 37°. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(12) bond length is 1.53 Å. The P(3)-O(9) bond length is 1.51 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 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(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. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Al(3) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Al(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Al(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Al(3) and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Al(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Al(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Al(3) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Al(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Al(3) and one P(3) atom. F(1) is bonded in a water-like geometry to two equivalent Al(2) atoms. Linkers: 6 [O]P([O])([O])=O. Metal clusters: 6 [Al]. The MOF has largest included sphere 5.77 A, density 1.68 g/cm3, surface area 2502.29 m2/g, accessible volume 0.31 cm3/g