Co2P3(O5F)2 crystallizes in the tetragonal P-4n2 space group. Co(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form CoO4 trigonal pyramids that share corners with three equivalent P(1)O3F tetrahedra. The Co(1)-O(1) bond length is 2.06 Å. The Co(1)-O(3) bond length is 1.94 Å. The Co(1)-O(4) bond length is 1.96 Å. The Co(1)-O(5) bond length is 1.94 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one F(1) atom to form PO3F tetrahedra that share corners with three equivalent Co(1)O4 trigonal pyramids. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-F(1) bond length is 1.54 Å. In the second P site, P(2) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. Both P(2)-O(1) bond lengths are 1.46 Å. Both P(2)-O(2) bond lengths are 1.82 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Co(1) and one P(2) atom. In the second O site, O(2) is bonded in a single-bond geometry to one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Co(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Co(1) and one P(1) atom. F(1) is bonded in a single-bond geometry to one P(1) atom. Linkers: 8 [O]P([O])(=O)F ,4 [O]P([O])([O])=O. Metal clusters: 8 [Co]. The MOF has largest included sphere 4.10 A, density 1.65 g/cm3, surface area 2837.88 m2/g, accessible volume 0.27 cm3/g