Ga4(PO4)5 crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form GaO4 tetrahedra that share  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(5)O4 tetrahedra. The Ga(1)-O(1) bond length is 1.81 Å. The Ga(1)-O(2) bond length is 1.82 Å. The Ga(1)-O(3) bond length is 1.82 Å. The Ga(1)-O(4) bond length is 1.83 Å. In the second Ga site, Ga(2) is bonded to one O(5), 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,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The Ga(2)-O(5) bond length is 1.83 Å. The Ga(2)-O(6) bond length is 1.85 Å. The Ga(2)-O(7) bond length is 1.82 Å. The Ga(2)-O(8) bond length is 1.84 Å. In the third Ga site, Ga(3) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(9) atom to form GaO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(5)O4 tetrahedra. The Ga(3)-O(10) bond length is 1.97 Å. The Ga(3)-O(11) bond length is 1.95 Å. The Ga(3)-O(12) bond length is 1.98 Å. The Ga(3)-O(13) bond length is 1.96 Å. The Ga(3)-O(14) bond length is 1.97 Å. The Ga(3)-O(9) bond length is 1.92 Å. In the fourth Ga site, Ga(4) is bonded to one O(15), one O(16), one O(17), and one O(18) atom to form GaO4 tetrahedra that share  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 Ga(4)-O(15) bond length is 1.83 Å. The Ga(4)-O(16) bond length is 1.83 Å. The Ga(4)-O(17) bond length is 1.82 Å. The Ga(4)-O(18) bond length is 1.83 Å. There are five inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(15), one O(19), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O4 tetrahedra,  a cornercorner with one Ga(2)O4 tetrahedra, and  a cornercorner with one Ga(4)O4 tetrahedra. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(15) bond length is 1.53 Å. The P(1)-O(19) bond length is 1.50 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(16), one O(4), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(3)O6 octahedra,  a cornercorner with one Ga(1)O4 tetrahedra,  a cornercorner with one Ga(2)O4 tetrahedra, and  a cornercorner with one Ga(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 30°. The P(2)-O(16) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.48 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(17), and one O(2) atom to form PO4 tetrahedra that share corners with two equivalent Ga(3)O6 octahedra,  a cornercorner with one Ga(1)O4 tetrahedra, and  a cornercorner with one Ga(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 9-49°. The P(3)-O(10) bond length is 1.52 Å. The P(3)-O(11) bond length is 1.50 Å. The P(3)-O(17) bond length is 1.55 Å. The P(3)-O(2) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(12), one O(18), one O(20), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(3)O6 octahedra,  a cornercorner with one Ga(2)O4 tetrahedra, and  a cornercorner with one Ga(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The P(4)-O(12) bond length is 1.50 Å. The P(4)-O(18) bond length is 1.53 Å. The P(4)-O(20) bond length is 1.54 Å. The P(4)-O(7) bond length is 1.53 Å. In the fifth P site, P(5) is bonded to one O(13), one O(14), one O(3), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ga(3)O6 octahedra,  a cornercorner with one Ga(1)O4 tetrahedra, and  a cornercorner with one Ga(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-44°. The P(5)-O(13) bond length is 1.52 Å. The P(5)-O(14) bond length is 1.51 Å. The P(5)-O(3) bond length is 1.56 Å. The P(5)-O(8) bond length is 1.57 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ga(1) 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(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(5) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ga(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 120 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(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Ga(2) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(5) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Ga(3) and one P(3) atom. In the eleventh O site, O(11) is bonded in a linear 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(3) and one P(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Ga(3) and one P(5) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Ga(4) and one P(1) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one Ga(4) and one P(2) atom. In the seventeenth O site, O(17) is bonded in a bent 120 degrees geometry to one Ga(4) and one P(3) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Ga(4) and one P(4) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one P(1) atom. In the twentieth O site, O(20) is bonded in a single-bond geometry to one P(4) atom. Linkers: 20 [O]P([O])([O])=O. Metal clusters: 16 [Ga]. The MOF has largest included sphere 5.34 A, density 2.14 g/cm3, surface area 2231.61 m2/g, accessible volume 0.25 cm3/g