Ga3P3O14 crystallizes in the orthorhombic Pbca space group. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(12), one O(14), one O(3), one O(8), and one O(9) atom to form GaO5 trigonal bipyramids that share  a cornercorner with one Ga(2)O6 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 52°. The Ga(1)-O(12) bond length is 1.87 Å. The Ga(1)-O(14) bond length is 1.96 Å. The Ga(1)-O(3) bond length is 1.89 Å. The Ga(1)-O(8) bond length is 1.85 Å. The Ga(1)-O(9) bond length is 1.95 Å. In the second Ga site, Ga(2) is bonded to one O(1), one O(10), one O(13), one O(14), one O(2), and one O(5) atom to form GaO6 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(1)O5 trigonal bipyramid, and  a cornercorner with one Ga(3)O5 trigonal bipyramid. The Ga(2)-O(1) bond length is 2.00 Å. The Ga(2)-O(10) bond length is 1.92 Å. The Ga(2)-O(13) bond length is 1.97 Å. The Ga(2)-O(14) bond length is 1.93 Å. The Ga(2)-O(2) bond length is 1.97 Å. The Ga(2)-O(5) bond length is 1.99 Å. In the third Ga site, Ga(3) is bonded to one O(11), one O(13), one O(4), one O(6), and one O(7) atom to form GaO5 trigonal bipyramids that share  a cornercorner with one Ga(2)O6 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 62°. The Ga(3)-O(11) bond length is 1.86 Å. The Ga(3)-O(13) bond length is 1.97 Å. The Ga(3)-O(4) bond length is 1.89 Å. The Ga(3)-O(6) bond length is 1.84 Å. The Ga(3)-O(7) bond length is 2.00 Å. There are three 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 corners with two equivalent Ga(2)O6 octahedra,  a cornercorner with one Ga(1)O5 trigonal bipyramid, and  a cornercorner with one Ga(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 52-53°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 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(2)O6 octahedra,  a cornercorner with one Ga(1)O5 trigonal bipyramid, and corners with two equivalent Ga(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 53°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.53 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)O6 octahedra,  a cornercorner with one Ga(3)O5 trigonal bipyramid, and corners with two equivalent Ga(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°. The P(3)-O(10) bond length is 1.54 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 1.53 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 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(2) and one P(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Ga(3) 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(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 distorted bent 150 degrees geometry to one Ga(3) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted 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(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Ga(3) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 120 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 Ga(3) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Ga(1) and one Ga(2) atom. Linkers: 24 [O]P([O])([O])=O. Metal clusters: 24 [Ga]. The MOF has largest included sphere 4.24 A, density 2.38 g/cm3, surface area 1854.85 m2/g, accessible volume 0.16 cm3/g