CsGa6P6(O13F2)2 crystallizes in the orthorhombic Pbcn space group. Cs(1) is bonded in a distorted q6 geometry to two equivalent O(12), two equivalent O(7), two equivalent O(9), and four equivalent O(13) atoms. Both Cs(1)-O(12) bond lengths are 3.28 Å. Both Cs(1)-O(7) bond lengths are 3.29 Å. Both Cs(1)-O(9) bond lengths are 3.10 Å. There are two shorter (3.34 Å) and two longer (3.36 Å) Cs(1)-O(13) bond lengths. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form GaO4F2 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Ga(2)O4F trigonal bipyramid, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The Ga(1)-O(1) bond length is 1.93 Å. The Ga(1)-O(2) bond length is 1.95 Å. The Ga(1)-O(3) bond length is 1.93 Å. The Ga(1)-O(4) bond length is 1.91 Å. The Ga(1)-F(1) bond length is 1.93 Å. The Ga(1)-F(2) bond length is 2.00 Å. In the second Ga site, Ga(2) is bonded to one O(5), one O(7), one O(8), one O(9), 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(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Ga(2)-O(5) bond length is 1.85 Å. The Ga(2)-O(7) bond length is 1.84 Å. The Ga(2)-O(8) bond length is 1.85 Å. The Ga(2)-O(9) bond length is 1.91 Å. The Ga(2)-F(1) bond length is 2.02 Å. In the third Ga site, Ga(3) is bonded to one O(10), one O(11), one O(12), one O(6), and one F(2) atom to form GaO4F trigonal bipyramids that share  a cornercorner with one Ga(1)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 59°. The Ga(3)-O(10) bond length is 2.01 Å. The Ga(3)-O(11) bond length is 1.82 Å. The Ga(3)-O(12) bond length is 1.84 Å. The Ga(3)-O(6) bond length is 1.84 Å. The Ga(3)-F(2) bond length is 2.02 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Ga(1)O4F2 octahedra,  a cornercorner with one Ga(2)O4F trigonal bipyramid, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 50°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.53 Å. The P(1)-O(5) 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(10), one O(11), one O(2), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O4F2 octahedra,  a cornercorner with one Ga(2)O4F trigonal bipyramid, and corners with two equivalent Ga(3)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 47°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(11) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(12), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O4F2 octahedra,  a cornercorner with one Ga(3)O4F trigonal bipyramid, and corners with two equivalent Ga(2)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(3) bond length is 1.53 Å. The P(3)-O(8) bond length is 1.53 Å. The P(3)-O(9) bond length is 1.53 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Ga(3) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Ga(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a 2-coordinate geometry to one Cs(1), one Ga(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Ga(3) and one P(2) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Ga(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a water-like geometry to two equivalent Cs(1) atoms. 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: 24 [O]P([O])([O])=O. Metal clusters: 4 [Cs] ,24 [Ga]. The MOF has largest included sphere 5.81 A, density 2.57 g/cm3, surface area 1946.16 m2/g, accessible volume 0.15 cm3/g