Ga4P5O23 crystallizes in the tetragonal I4_1/a space group. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(1), one O(3), one O(5), one O(9), and two equivalent O(8) atoms to form GaO6 octahedra that share corners with two equivalent Ga(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-57°. The Ga(1)-O(1) bond length is 1.93 Å. The Ga(1)-O(3) bond length is 1.91 Å. The Ga(1)-O(5) bond length is 1.89 Å. The Ga(1)-O(9) bond length is 1.92 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) Ga(1)-O(8) bond length. In the second Ga site, Ga(2) is bonded to one O(11), one O(12), one O(2), one O(4), one O(7), and one O(8) atom to form GaO6 octahedra that share  a cornercorner with one Ga(2)O6 octahedra, corners with two equivalent Ga(1)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 range from 44-57°. The Ga(2)-O(11) bond length is 1.95 Å. The Ga(2)-O(12) bond length is 1.94 Å. The Ga(2)-O(2) bond length is 1.97 Å. The Ga(2)-O(4) bond length is 1.96 Å. The Ga(2)-O(7) bond length is 1.94 Å. The Ga(2)-O(8) bond length is 2.12 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(11), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(2)O6 octahedra and corners with two equivalent Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-56°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(10) bond length is 1.52 Å. The P(1)-O(11) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-43°. The P(2)-O(2) bond length is 1.52 Å. The P(2)-O(4) bond length is 1.52 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.58 Å. In the third P site, P(3) is bonded to two equivalent O(7) and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Ga(1)O6 octahedra and corners with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-56°. Both P(3)-O(7) bond lengths are 1.53 Å. Both P(3)-O(9) bond lengths are 1.53 Å. There are twelve inequivalent O sites. In the first O site, O(12) is bonded in a bent 150 degrees geometry to two equivalent Ga(2) atoms. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the third O site, O(2) is bonded in a bent 150 degrees geometry to one Ga(2) and one P(2) atom. In the fourth O site, O(3) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ga(2) and one P(2) atom. In the sixth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Ga(1) and one P(2) atom. In the seventh O site, O(6) is bonded in a single-bond geometry to one P(2) atom. In the eighth O site, O(7) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(3) atom. In the ninth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ga(2) and two equivalent Ga(1) atoms. In the tenth O site, O(9) is bonded in a bent 120 degrees geometry to one Ga(1) and one P(3) atom. In the eleventh O site, O(10) is bonded in a single-bond geometry to one P(1) atom. In the twelfth O site, O(11) is bonded in a bent 120 degrees geometry to one Ga(2) and one P(1) atom. Linkers: 40 [O]P([O])([O])=O. Metal clusters: 32 [Ga]. The MOF has largest included sphere 9.54 A, density 1.58 g/cm3, surface area 2138.99 m2/g, accessible volume 0.37 cm3/g