Ga2P2O8F crystallizes in the orthorhombic Pbcn space group. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(12), one O(16), one O(2), one O(5), and one F(2) atom to form GaO4F trigonal bipyramids that share  a cornercorner with one Ga(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The Ga(1)-O(12) bond length is 1.85 Å. The Ga(1)-O(16) bond length is 1.84 Å. The Ga(1)-O(2) bond length is 1.85 Å. The Ga(1)-O(5) bond length is 1.94 Å. The Ga(1)-F(2) bond length is 2.00 Å. In the second Ga site, Ga(2) is bonded to one O(1), one O(13), one O(15), one O(9), one F(1), and one F(2) atom to form GaO4F2 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Ga(1)O4F trigonal bipyramid, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The Ga(2)-O(1) bond length is 1.94 Å. The Ga(2)-O(13) bond length is 1.93 Å. The Ga(2)-O(15) bond length is 1.91 Å. The Ga(2)-O(9) bond length is 1.94 Å. The Ga(2)-F(1) bond length is 2.01 Å. The Ga(2)-F(2) bond length is 1.97 Å. In the third Ga site, Ga(3) is bonded to one O(10), one O(11), one O(14), one O(4), and one F(1) atom to form GaO4F trigonal bipyramids that share  a cornercorner with one Ga(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The Ga(3)-O(10) bond length is 1.84 Å. The Ga(3)-O(11) bond length is 2.00 Å. The Ga(3)-O(14) bond length is 1.83 Å. The Ga(3)-O(4) bond length is 1.85 Å. The Ga(3)-F(1) bond length is 2.00 Å. In the fourth Ga site, Ga(4) is bonded to one O(3), one O(6), one O(7), and one O(8) atom to form GaO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Ga(4)-O(3) bond length is 1.80 Å. The Ga(4)-O(6) bond length is 1.79 Å. The Ga(4)-O(7) bond length is 1.81 Å. The Ga(4)-O(8) bond length is 1.83 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(2)O4F2 octahedra,  a cornercorner with one Ga(4)O4 tetrahedra,  a cornercorner with one Ga(1)O4F trigonal bipyramid, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 45°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Ga(4)O4 tetrahedra and  a cornercorner with one Ga(1)O4F trigonal bipyramid. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.55 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 Ga(2)O4F2 octahedra,  a cornercorner with one Ga(1)O4F trigonal bipyramid, and corners with two equivalent Ga(3)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 46°. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(11) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(9) bond length is 1.51 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(16) atom to form PO4 tetrahedra that share corners with two equivalent Ga(2)O4F2 octahedra,  a cornercorner with one Ga(1)O4F trigonal bipyramid, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 50-52°. The P(4)-O(13) bond length is 1.53 Å. The P(4)-O(14) bond length is 1.54 Å. The P(4)-O(15) bond length is 1.54 Å. The P(4)-O(16) bond length is 1.56 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Ga(2) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Ga(4) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ga(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Ga(4) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Ga(4) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Ga(4) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Ga(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Ga(3) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ga(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Ga(3) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(4) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one Ga(2) and one Ga(3) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ga(1) and one Ga(2) atom. Linkers: 32 [O]P([O])([O])=O. Metal clusters: 32 [Ga]. The MOF has largest included sphere 9.39 A, density 1.91 g/cm3, surface area 1979.03 m2/g, accessible volume 0.30 cm3/g