Na14Mo24P17O104 crystallizes in the cubic Pn-3 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(10), one O(2), one O(9), and two equivalent O(6) atoms to form distorted NaO5 trigonal bipyramids 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, corners with two equivalent Na(1)O5 trigonal bipyramids, and edges with two equivalent Na(1)O5 trigonal bipyramids. The Na(1)-O(10) bond length is 2.39 Å. The Na(1)-O(2) bond length is 2.52 Å. The Na(1)-O(9) bond length is 2.31 Å. There is one shorter (2.34 Å) and one longer (2.49 Å) Na(1)-O(6) bond length. In the second Na site, Na(2) is bonded in an octahedral geometry to six equivalent O(1) atoms. All Na(2)-O(1) bond lengths are 2.34 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. The Mo(1)-O(1) bond length is 1.96 Å. The Mo(1)-O(2) bond length is 1.93 Å. The Mo(1)-O(3) bond length is 2.30 Å. The Mo(1)-O(4) bond length is 2.11 Å. The Mo(1)-O(5) bond length is 2.09 Å. In the second Mo site, Mo(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(8) atom. The Mo(2)-O(1) bond length is 1.95 Å. The Mo(2)-O(2) bond length is 1.96 Å. The Mo(2)-O(3) bond length is 2.25 Å. The Mo(2)-O(5) bond length is 2.15 Å. The Mo(2)-O(8) bond length is 2.11 Å. There are three inequivalent P sites. In the first P site, P(2) is bonded to one O(9) and three equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Na(1)O5 trigonal bipyramids. The P(2)-O(9) bond length is 1.49 Å. All P(2)-O(3) bond lengths are 1.56 Å. In the second P site, P(1) is bonded to one O(4), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O5 trigonal bipyramids. The P(1)-O(4) bond length is 1.51 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.52 Å. In the third P site, P(3) is bonded to four equivalent O(10) atoms to form PO4 tetrahedra that share corners with twelve equivalent Na(1)O5 trigonal bipyramids. All P(3)-O(10) bond lengths are 1.55 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(2), one Mo(1), and one Mo(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Mo(1), and one Mo(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Mo(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one P(1) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one Mo(2) and one P(1) atom. In the ninth O site, O(9) is bonded in a tetrahedral geometry to three equivalent Na(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Na(1) and one P(3) atom. Linkers: 34 [O]P([O])([O])=O. Metal clusters: 28 [Na] ,48 [Mo]. The MOF has largest included sphere 6.96 A, density 1.88 g/cm3, surface area 1376.92 m2/g, accessible volume 0.22 cm3/g