NaZnP2H5(CO3)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.80 Å. The Na(1)-O(2) bond length is 2.31 Å. The Na(1)-O(3) bond length is 2.43 Å. The Na(1)-O(4) bond length is 2.40 Å. The Na(1)-O(5) bond length is 2.43 Å. The Na(1)-O(6) bond length is 2.35 Å. Zn(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form ZnO4 tetrahedra that share  a cornercorner with one P(1)CO3 tetrahedra and corners with three equivalent P(2)CO3 tetrahedra. The Zn(1)-O(1) bond length is 1.97 Å. The Zn(1)-O(4) bond length is 1.94 Å. The Zn(1)-O(5) bond length is 1.95 Å. The Zn(1)-O(6) bond length is 1.97 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a distorted water-like geometry to one P(1), one H(2), and one H(3) atom. The C(1)-P(1) bond length is 1.81 Å. The C(1)-H(2) bond length is 1.10 Å. The C(1)-H(3) bond length is 1.10 Å. In the second C site, C(2) is bonded in a distorted water-like geometry to one P(2), one H(4), and one H(5) atom. The C(2)-P(2) bond length is 1.81 Å. The C(2)-H(4) bond length is 1.10 Å. The C(2)-H(5) bond length is 1.10 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one C(1), one O(1), one O(2), and one O(3) atom to form PCO3 tetrahedra that share  a cornercorner with one Zn(1)O4 tetrahedra. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.60 Å. In the second P site, P(2) is bonded to one C(2), one O(4), one O(5), and one O(6) atom to form PCO3 tetrahedra that share corners with three equivalent Zn(1)O4 tetrahedra. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.54 Å. There are five inequivalent H sites. In the first H site, H(5) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(1) is bonded in a linear geometry to one O(2) and one O(3) atom. The H(1)-O(2) bond length is 1.54 Å. The H(1)-O(3) bond length is 1.03 Å. In the third H site, H(2) is bonded in a single-bond geometry to one C(1) atom. In the fourth H site, H(3) is bonded in a single-bond geometry to one C(1) atom. In the fifth H site, H(4) is bonded in a single-bond geometry to one C(2) atom. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(2) atom. In the second O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Zn(1), and one P(1) atom. In the third O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Zn(1), and one P(2) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one P(1), and one H(1) atom. In the fifth O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one P(1), and one H(1) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(1), one Zn(1), and one P(2) atom. Linkers: 4 [O]P([O])(=O)CCP([O])(=O)O. Metal clusters: 4 [Na] ,4 [Zn]. The MOF has largest included sphere 1.63 A, density 2.50 g/cm3, surface area 2347.19 m2/g, accessible volume 0.03 cm3/g