Ga5P5O21F crystallizes in the monoclinic P2_1 space group. There are ten inequivalent Ga sites. In the first Ga site, Ga(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one O(17), and one O(4) atom. The Ga(1)-O(1) bond length is 1.93 Å. The Ga(1)-O(17) bond length is 1.85 Å. The Ga(1)-O(4) bond length is 1.90 Å. In the second Ga site, Ga(2) is bonded in a 4-coordinate geometry to one O(10), one O(19), one O(2), one O(5), and one F(1) atom. The Ga(2)-O(10) bond length is 1.83 Å. The Ga(2)-O(19) bond length is 1.85 Å. The Ga(2)-O(2) bond length is 1.80 Å. The Ga(2)-O(5) bond length is 1.84 Å. The Ga(2)-F(1) bond length is 2.47 Å. In the third Ga site, Ga(3) is bonded to one O(11), one O(3), one O(6), one O(9), and one F(1) atom to form GaO4F trigonal bipyramids that share  a cornercorner with one Ga(4)O5F 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 60°. The Ga(3)-O(11) bond length is 1.84 Å. The Ga(3)-O(3) bond length is 1.81 Å. The Ga(3)-O(6) bond length is 1.81 Å. The Ga(3)-O(9) bond length is 1.89 Å. The Ga(3)-F(1) bond length is 2.29 Å. In the fourth Ga site, Ga(4) is bonded to one O(18), one O(20), one O(36), one O(42), one O(8), and one F(1) atom to form GaO5F octahedra that share  a cornercorner with one Ga(10)O6 octahedra,  a cornercorner with one Ga(5)O6 octahedra,  a cornercorner with one P(10)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 56-58°. The Ga(4)-O(18) bond length is 1.98 Å. The Ga(4)-O(20) bond length is 1.94 Å. The Ga(4)-O(36) bond length is 1.97 Å. The Ga(4)-O(42) bond length is 2.10 Å. The Ga(4)-O(8) bond length is 1.89 Å. The Ga(4)-F(1) bond length is 2.02 Å. In the fifth Ga site, Ga(5) is bonded to one O(12), one O(13), one O(14), one O(15), one O(41), and one O(42) atom to form GaO6 octahedra that share  a cornercorner with one Ga(4)O5F octahedra,  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one P(10)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(9)O4 tetrahedra, and  an edgeedge with one Ga(10)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-58°. The Ga(5)-O(12) bond length is 1.91 Å. The Ga(5)-O(13) bond length is 1.94 Å. The Ga(5)-O(14) bond length is 1.92 Å. The Ga(5)-O(15) bond length is 1.95 Å. The Ga(5)-O(41) bond length is 2.13 Å. The Ga(5)-O(42) bond length is 2.09 Å. In the sixth Ga site, Ga(6) is bonded in a trigonal non-coplanar geometry to one O(21), one O(24), and one O(37) atom. The Ga(6)-O(21) bond length is 1.81 Å. The Ga(6)-O(24) bond length is 1.82 Å. The Ga(6)-O(37) bond length is 1.85 Å. In the seventh Ga site, Ga(7) is bonded to one O(22), one O(25), one O(30), one O(39), and one F(2) atom to form GaO4F trigonal bipyramids that share  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  a cornercorner with one P(9)O4 tetrahedra. The corner-sharing octahedral tilt angles are 59°. The Ga(7)-O(22) bond length is 1.85 Å. The Ga(7)-O(25) bond length is 1.88 Å. The Ga(7)-O(30) bond length is 1.81 Å. The Ga(7)-O(39) bond length is 1.89 Å. The Ga(7)-F(2) bond length is 2.09 Å. In the eighth Ga site, Ga(8) is bonded to one O(23), one O(26), one O(29), and one O(31) atom to form GaO4 tetrahedra that share  a cornercorner with one P(6)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  a cornercorner with one P(9)O4 tetrahedra. The Ga(8)-O(23) bond length is 1.86 Å. The Ga(8)-O(26) bond length is 1.85 Å. The Ga(8)-O(29) bond length is 1.87 Å. The Ga(8)-O(31) bond length is 1.83 Å. In the ninth Ga site, Ga(9) is bonded to one O(16), one O(28), one O(38), one O(40), one O(41), and one F(2) atom to form GaO5F octahedra that share  a cornercorner with one Ga(10)O6 octahedra,  a cornercorner with one Ga(5)O6 octahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(7)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra,  a cornercorner with one P(9)O4 tetrahedra, and  a cornercorner with one Ga(7)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 56-58°. The Ga(9)-O(16) bond length is 1.95 Å. The Ga(9)-O(28) bond length is 1.95 Å. The Ga(9)-O(38) bond length is 1.92 Å. The Ga(9)-O(40) bond length is 1.93 Å. The Ga(9)-O(41) bond length is 2.05 Å. The Ga(9)-F(2) bond length is 2.09 Å. In the tenth Ga site, Ga(10) is bonded to one O(32), one O(33), one O(34), one O(35), one O(41), and one O(42) atom to form GaO6 octahedra that share  a cornercorner with one Ga(4)O5F octahedra,  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one P(10)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(8)O4 tetrahedra, and  an edgeedge with one Ga(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-58°. The Ga(10)-O(32) bond length is 1.88 Å. The Ga(10)-O(33) bond length is 1.95 Å. The Ga(10)-O(34) bond length is 1.90 Å. The Ga(10)-O(35) bond length is 1.87 Å. The Ga(10)-O(41) bond length is 2.13 Å. The Ga(10)-O(42) bond length is 2.14 Å. There are ten inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(24), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(3)O4F trigonal bipyramid. The P(1)-O(1) bond length is 1.48 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(24) bond length is 1.49 Å. The P(1)-O(3) 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  a cornercorner with one Ga(4)O5F octahedra and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.49 Å. The P(2)-O(8) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(19), and one O(20) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(4)O5F octahedra,  a cornercorner with one Ga(5)O6 octahedra, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-48°. The P(3)-O(11) bond length is 1.51 Å. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(19) bond length is 1.56 Å. The P(3)-O(20) bond length is 1.50 Å. In the fourth P site, P(4) is bonded to one O(10), one O(18), one O(34), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(4)O5F octahedra,  a cornercorner with one Ga(10)O6 octahedra, and  a cornercorner with one Ga(3)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-47°. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(18) bond length is 1.50 Å. The P(4)-O(34) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.51 Å. In the fifth P site, P(5) is bonded to one O(15), one O(16), one O(17), and one O(33) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one Ga(10)O6 octahedra, and  a cornercorner with one Ga(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. The P(5)-O(15) bond length is 1.50 Å. The P(5)-O(16) bond length is 1.54 Å. The P(5)-O(17) bond length is 1.52 Å. The P(5)-O(33) bond length is 1.55 Å. In the sixth P site, P(6) is bonded to one O(21), one O(22), one O(23), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(8)O4 tetrahedra and  a cornercorner with one Ga(7)O4F trigonal bipyramid. The P(6)-O(21) bond length is 1.59 Å. The P(6)-O(22) bond length is 1.51 Å. The P(6)-O(23) bond length is 1.51 Å. The P(6)-O(4) bond length is 1.53 Å. In the seventh P site, P(7) is bonded to one O(25), one O(26), one O(27), and one O(28) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one Ga(8)O4 tetrahedra, and  a cornercorner with one Ga(7)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 56°. The P(7)-O(25) bond length is 1.58 Å. The P(7)-O(26) bond length is 1.55 Å. The P(7)-O(27) bond length is 1.49 Å. The P(7)-O(28) bond length is 1.50 Å. In the eighth P site, P(8) is bonded to one O(31), one O(32), one O(39), and one O(40) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one Ga(10)O6 octahedra,  a cornercorner with one Ga(8)O4 tetrahedra, and  a cornercorner with one Ga(7)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-48°. The P(8)-O(31) bond length is 1.53 Å. The P(8)-O(32) bond length is 1.52 Å. The P(8)-O(39) bond length is 1.52 Å. The P(8)-O(40) bond length is 1.55 Å. In the ninth P site, P(9) is bonded to one O(14), one O(29), one O(30), and one O(38) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(9)O5F octahedra,  a cornercorner with one Ga(5)O6 octahedra,  a cornercorner with one Ga(8)O4 tetrahedra, and  a cornercorner with one Ga(7)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 48-49°. The P(9)-O(14) bond length is 1.54 Å. The P(9)-O(29) bond length is 1.57 Å. The P(9)-O(30) bond length is 1.56 Å. The P(9)-O(38) bond length is 1.51 Å. In the tenth P site, P(10) is bonded to one O(13), one O(35), one O(36), and one O(37) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(4)O5F octahedra,  a cornercorner with one Ga(10)O6 octahedra, and  a cornercorner with one Ga(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. The P(10)-O(13) bond length is 1.51 Å. The P(10)-O(35) bond length is 1.57 Å. The P(10)-O(36) bond length is 1.53 Å. The P(10)-O(37) bond length is 1.55 Å. There are forty-two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ga(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ga(3) 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(6) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ga(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(2) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one P(2) atom. In the eighth O site, O(8) is bonded in a 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 150 degrees geometry to one Ga(3) and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a 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 120 degrees geometry to one Ga(5) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Ga(5) and one P(10) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Ga(5) and one P(9) atom. In the fifteenth O site, O(15) is bonded in a bent 120 degrees geometry to one Ga(5) and one P(5) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Ga(9) and one P(5) atom. In the seventeenth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one Ga(1) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 120 degrees geometry to one Ga(4) and one P(4) atom. In the nineteenth O site, O(19) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(3) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Ga(4) and one P(3) atom. In the twenty-first O site, O(21) is bonded in a bent 120 degrees geometry to one Ga(6) and one P(6) atom. In the twenty-second O site, O(22) is bonded in a distorted bent 120 degrees geometry to one Ga(7) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted bent 150 degrees geometry to one Ga(8) and one P(6) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Ga(6) and one P(1) atom. In the twenty-fifth O site, O(25) is bonded in a bent 120 degrees geometry to one Ga(7) and one P(7) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one Ga(8) and one P(7) atom. In the twenty-seventh O site, O(27) is bonded in a single-bond geometry to one P(7) atom. In the twenty-eighth O site, O(28) is bonded in a bent 120 degrees geometry to one Ga(9) and one P(7) atom. In the twenty-ninth O site, O(29) is bonded in a bent 120 degrees geometry to one Ga(8) and one P(9) atom. In the thirtieth O site, O(30) is bonded in a bent 120 degrees geometry to one Ga(7) and one P(9) atom. In the thirty-first O site, O(31) is bonded in a bent 120 degrees geometry to one Ga(8) and one P(8) atom. In the thirty-second O site, O(32) is bonded in a bent 120 degrees geometry to one Ga(10) and one P(8) atom. In the thirty-third O site, O(33) is bonded in a bent 120 degrees geometry to one Ga(10) and one P(5) atom. In the thirty-fourth O site, O(34) is bonded in a distorted bent 150 degrees geometry to one Ga(10) and one P(4) atom. In the thirty-fifth O site, O(35) is bonded in a bent 120 degrees geometry to one Ga(10) and one P(10) atom. In the thirty-sixth O site, O(36) is bonded in a bent 120 degrees geometry to one Ga(4) and one P(10) atom. In the thirty-seventh O site, O(37) is bonded in a distorted bent 120 degrees geometry to one Ga(6) and one P(10) atom. In the thirty-eighth O site, O(38) is bonded in a distorted bent 120 degrees geometry to one Ga(9) and one P(9) atom. In the thirty-ninth O site, O(39) is bonded in a distorted bent 150 degrees geometry to one Ga(7) and one P(8) atom. In the fortieth O site, O(40) is bonded in a distorted bent 150 degrees geometry to one Ga(9) and one P(8) atom. In the forty-first O site, O(41) is bonded in a trigonal planar geometry to one Ga(10), one Ga(5), and one Ga(9) atom. In the forty-second O site, O(42) is bonded in a trigonal planar geometry to one Ga(10), one Ga(4), and one Ga(5) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Ga(2), one Ga(3), and one Ga(4) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Ga(7) and one Ga(9) atom. Linkers: 20 [O]P([O])([O])=O. Metal clusters: 20 [Ga]. The MOF has largest included sphere 5.64 A, density 1.90 g/cm3, surface area 1948.83 m2/g, accessible volume 0.30 cm3/g