Ga5P5(O5F)4 crystallizes in the orthorhombic Pccn space group. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(4), one O(7), one O(8), one O(9), one F(1), and one F(2) atom to form GaO4F2 octahedra that share  a cornercorner with one Ga(3)O4F2 octahedra,  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  a cornercorner with one Ga(2)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 48°. The Ga(1)-O(4) bond length is 1.98 Å. The Ga(1)-O(7) bond length is 1.87 Å. The Ga(1)-O(8) bond length is 1.96 Å. The Ga(1)-O(9) bond length is 1.92 Å. The Ga(1)-F(1) bond length is 1.93 Å. The Ga(1)-F(2) bond length is 2.03 Å. In the second Ga site, Ga(2) is bonded to one O(10), one O(3), one O(5), one O(6), and one F(1) atom to form GaO4F trigonal bipyramids that share  a cornercorner with one Ga(1)O4F2 octahedra,  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 corner-sharing octahedral tilt angles are 61°. The Ga(2)-O(10) bond length is 1.93 Å. The Ga(2)-O(3) bond length is 1.83 Å. The Ga(2)-O(5) bond length is 1.86 Å. The Ga(2)-O(6) bond length is 1.87 Å. The Ga(2)-F(1) bond length is 2.01 Å. In the third Ga site, Ga(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form GaO4F2 octahedra that share corners with two equivalent Ga(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. Both Ga(3)-O(1) bond lengths are 1.97 Å. Both Ga(3)-O(2) bond lengths are 1.91 Å. Both Ga(3)-F(2) bond lengths are 1.99 Å. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent O(5) and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Ga(1)O4F2 octahedra and corners with two equivalent Ga(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 49°. Both P(3)-O(5) bond lengths are 1.55 Å. Both P(3)-O(9) bond lengths are 1.52 Å. In the second P site, P(1) is bonded to one O(10), one O(2), one O(3), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O4F2 octahedra,  a cornercorner with one Ga(3)O4F2 octahedra, and corners with two equivalent Ga(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 36-46°. The P(1)-O(10) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.52 Å. In the third P site, P(2) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(3)O4F2 octahedra, corners with two equivalent Ga(1)O4F2 octahedra, and  a cornercorner with one Ga(2)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 48-55°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.52 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ga(3) and one P(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ga(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ga(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Ga(2) and one P(1) 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(1) and one Ga(2) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ga(1) and one Ga(3) atom. Linkers: 20 [O]P([O])([O])=O. Metal clusters: 20 [Ga]. The MOF has largest included sphere 4.30 A, density 2.43 g/cm3, surface area 1909.53 m2/g, accessible volume 0.20 cm3/g