Co2P2O7F crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form CoO4 trigonal pyramids that share corners with two equivalent P(2)O3F tetrahedra and corners with two equivalent P(1)O4 tetrahedra. The Co(1)-O(3) bond length is 1.96 Å. The Co(1)-O(4) bond length is 2.04 Å. Both Co(1)-O(2) bond lengths are 1.97 Å. In the second Co site, Co(2) is bonded to two equivalent O(1) and two equivalent O(5) atoms to form CoO4 trigonal pyramids that share corners with two equivalent P(2)O3F tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Co(2)O4 trigonal pyramid. Both Co(2)-O(1) bond lengths are 1.94 Å. There is one shorter (2.00 Å) and one longer (2.13 Å) Co(2)-O(5) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Co(1)O4 trigonal pyramids and corners with two equivalent Co(2)O4 trigonal pyramids. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.51 Å. Both P(1)-O(1) bond lengths are 1.53 Å. In the second P site, P(2) is bonded to one O(5), two equivalent O(2), and one F(1) atom to form PO3F tetrahedra that share corners with two equivalent Co(1)O4 trigonal pyramids and corners with two equivalent Co(2)O4 trigonal pyramids. The P(2)-O(5) bond length is 1.54 Å. Both P(2)-O(2) bond lengths are 1.53 Å. The P(2)-F(1) bond length is 1.55 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(2) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Co(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Co(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Co(2) and one P(2) atom. F(1) is bonded in a single-bond geometry to one P(2) atom. Linkers: 8 [O]P([O])(=O)F ,8 [O]P([O])([O])=O. Metal clusters: 16 [Co]. The MOF has largest included sphere 3.87 A, density 2.10 g/cm3, surface area 2089.40 m2/g, accessible volume 0.18 cm3/g