NaZnPH2(CO3)2 crystallizes in the orthorhombic Pbca space group. Na(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 Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(2) bond length is 2.33 Å. The Na(1)-O(3) bond length is 2.32 Å. The Na(1)-O(4) bond length is 2.45 Å. The Na(1)-O(5) bond length is 2.39 Å. Zn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form ZnO6 octahedra that share  a cornercorner with one C(1)PHCO tetrahedra and corners with three equivalent P(1)CO3 tetrahedra. The Zn(1)-O(1) bond length is 2.16 Å. The Zn(1)-O(2) bond length is 2.01 Å. The Zn(1)-O(3) bond length is 2.03 Å. The Zn(1)-O(4) bond length is 2.26 Å. The Zn(1)-O(5) bond length is 2.17 Å. The Zn(1)-O(6) bond length is 2.16 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded to one C(2), one P(1), one H(2), and one O(4) atom to form distorted CPHCO tetrahedra that share  a cornercorner with one Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 70°. The C(1)-C(2) bond length is 1.52 Å. The C(1)-P(1) bond length is 1.86 Å. The C(1)-H(2) bond length is 1.10 Å. The C(1)-O(4) bond length is 1.43 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(5), and one O(6) atom. The C(2)-O(5) bond length is 1.27 Å. The C(2)-O(6) bond length is 1.28 Å. 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 corners with three equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.53 Å. There are two inequivalent H sites. In the first H site, H(2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(1) is bonded in a linear geometry to one O(4) and one O(6) atom. The H(1)-O(4) bond length is 1.01 Å. The H(1)-O(6) bond length is 1.54 Å. There are six inequivalent O sites. In the first O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Zn(1), and one P(1) atom. In the second O site, O(6) is bonded in a distorted trigonal planar geometry to one Zn(1), one C(2), and one H(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Zn(1), one C(1), and one H(1) atom. In the fifth O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(1) atom. In the sixth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Zn(1), and one C(2) atom. Linkers: 4 [O]C(=O)[C@@H](O)P([O])([O])=O ,4 [O]C(=O)[C@H](O)P([O])([O])=O. Metal clusters: 8 [Na] ,8 [Zn]. The MOF has largest included sphere 1.17 A, density 3.00 g/cm3, surface area 1203.99 m2/g, accessible volume 0.03 cm3/g