Al4(PO4)5 crystallizes in the triclinic P1 space group. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(12), one O(13), one O(16), one O(17), and one O(5) atom to form AlO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Al(1)-O(12) bond length is 1.79 Å. The Al(1)-O(13) bond length is 1.85 Å. The Al(1)-O(16) bond length is 1.78 Å. The Al(1)-O(17) bond length is 1.90 Å. The Al(1)-O(5) bond length is 1.81 Å. In the second Al site, Al(2) is bonded to one O(1), one O(10), one O(3), and one O(9) 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(5)O4 tetrahedra. The Al(2)-O(1) bond length is 1.74 Å. The Al(2)-O(10) bond length is 1.75 Å. The Al(2)-O(3) bond length is 1.75 Å. The Al(2)-O(9) bond length is 1.72 Å. In the third Al site, Al(3) is bonded to one O(11), one O(14), one O(18), one O(19), and one O(8) atom to form AlO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Al(3)-O(11) bond length is 1.79 Å. The Al(3)-O(14) bond length is 1.83 Å. The Al(3)-O(18) bond length is 1.94 Å. The Al(3)-O(19) bond length is 1.82 Å. The Al(3)-O(8) bond length is 1.78 Å. In the fourth Al site, Al(4) is bonded to one O(2), one O(4), one O(6), and one O(7) atom to form AlO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Al(4)-O(2) bond length is 1.72 Å. The Al(4)-O(4) bond length is 1.75 Å. The Al(4)-O(6) bond length is 1.74 Å. The Al(4)-O(7) bond length is 1.73 Å. There are five inequivalent P sites. In the first P site, P(1) is bonded to one O(13), one O(19), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Al(4)O4 tetrahedra,  a cornercorner with one Al(1)O5 trigonal bipyramid, and  a cornercorner with one Al(3)O5 trigonal bipyramid. The P(1)-O(13) bond length is 1.49 Å. The P(1)-O(19) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(1), one O(15), one O(2), and one O(20) atom to form PO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra and  a cornercorner with one Al(4)O4 tetrahedra. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(15) bond length is 1.49 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(20) bond length is 1.59 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(17), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Al(2)O4 tetrahedra,  a cornercorner with one Al(1)O5 trigonal bipyramid, and corners with two equivalent Al(3)O5 trigonal bipyramids. 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(17) bond length is 1.53 Å. The P(3)-O(8) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(12), one O(18), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Al(4)O4 tetrahedra,  a cornercorner with one Al(3)O5 trigonal bipyramid, and corners with two equivalent Al(1)O5 trigonal bipyramids. The P(4)-O(12) bond length is 1.52 Å. The P(4)-O(18) bond length is 1.53 Å. The P(4)-O(5) bond length is 1.51 Å. The P(4)-O(7) bond length is 1.56 Å. In the fifth P site, P(5) is bonded to one O(14), one O(16), one O(3), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Al(2)O4 tetrahedra,  a cornercorner with one Al(1)O5 trigonal bipyramid, and  a cornercorner with one Al(3)O5 trigonal bipyramid. The P(5)-O(14) bond length is 1.51 Å. The P(5)-O(16) bond length is 1.53 Å. The P(5)-O(3) bond length is 1.55 Å. The P(5)-O(9) bond length is 1.53 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Al(2) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Al(4) and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Al(2) and one P(5) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Al(4) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Al(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Al(4) and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Al(4) and one P(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Al(3) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Al(2) and one P(5) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Al(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Al(3) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Al(1) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Al(1) and one P(1) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Al(3) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one P(2) atom. In the sixteenth O site, O(16) is bonded in a bent 150 degrees geometry to one Al(1) and one P(5) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Al(1) and one P(3) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Al(3) and one P(4) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Al(3) and one P(1) atom. In the twentieth O site, O(20) is bonded in a single-bond geometry to one P(2) atom. Linkers: 5 [O]P([O])([O])=O. Metal clusters: 4 [Al]. The MOF has largest included sphere 5.31 A, density 1.75 g/cm3, surface area 2564.46 m2/g, accessible volume 0.21 cm3/g