NaBe2P2H2O9 crystallizes in the trigonal P-31c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to six equivalent O(3) atoms to form distorted NaO6 pentagonal pyramids that share corners with six equivalent Be(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All Na(1)-O(3) bond lengths are 2.44 Å. In the second Na site, Na(2) is bonded in a 9-coordinate geometry to three equivalent H(1), three equivalent O(3), and three equivalent O(5) atoms. All Na(2)-H(1) bond lengths are 2.51 Å. All Na(2)-O(3) bond lengths are 2.43 Å. All Na(2)-O(5) bond lengths are 2.49 Å. Be(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form BeO4 tetrahedra that share  a cornercorner with one Na(1)O6 pentagonal pyramid and corners with four equivalent P(1)O4 tetrahedra. The Be(1)-O(1) bond length is 1.58 Å. The Be(1)-O(2) bond length is 1.64 Å. The Be(1)-O(3) bond length is 1.65 Å. The Be(1)-O(4) bond length is 1.62 Å. 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  a cornercorner with one Na(1)O6 pentagonal pyramid and corners with four equivalent Be(1)O4 tetrahedra. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.51 Å. H(1) is bonded in a single-bond geometry to one Na(2) and one O(5) atom. The H(1)-O(5) bond length is 0.83 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Be(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Be(1) and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Be(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Be(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to two equivalent Na(2) and two equivalent H(1) atoms. Linkers: 12 [O]P([O])([O])=O ,6 O. Metal clusters: 6 [Na] ,12 [Be]. The MOF has largest included sphere 6.68 A, density 1.77 g/cm3, surface area 1887.31 m2/g, accessible volume 0.21 cm3/g