NaZn2H21(C9O4)3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in an octahedral geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. Both Na(1)-O(2) bond lengths are 2.41 Å. Both Na(1)-O(3) bond lengths are 2.35 Å. Both Na(1)-O(6) bond lengths are 2.52 Å. Zn(1) is bonded in a distorted trigonal planar geometry to one O(2), one O(4), and one O(5) atom. The Zn(1)-O(2) bond length is 1.98 Å. The Zn(1)-O(4) bond length is 1.98 Å. The Zn(1)-O(5) bond length is 1.97 Å. There are fifteen inequivalent C sites. In the first C site, C(13) is bonded in a distorted single-bond geometry to two equivalent C(11) and one H(11) atom. Both C(13)-C(11) bond lengths are 1.39 Å. The C(13)-H(11) bond length is 0.93 Å. In the second C site, C(14) is bonded in a trigonal planar geometry to one C(15) and two equivalent C(12) atoms. The C(14)-C(15) bond length is 1.52 Å. Both C(14)-C(12) bond lengths are 1.38 Å. In the third C site, C(15) is bonded in a 6-coordinate geometry to one C(14), two equivalent H(10), two equivalent H(8), and two equivalent H(9) atoms. Both C(15)-H(10) bond lengths are 0.96 Å. Both C(15)-H(8) bond lengths are 0.96 Å. Both C(15)-H(9) bond lengths are 0.96 Å. In the fourth C site, C(1) is bonded in a distorted single-bond geometry to one C(3), one C(8), and one H(1) atom. The C(1)-C(3) bond length is 1.40 Å. The C(1)-C(8) bond length is 1.38 Å. The C(1)-H(1) bond length is 0.93 Å. In the fifth C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(2) atom. The C(2)-C(3) bond length is 1.51 Å. The C(2)-O(1) bond length is 1.24 Å. The C(2)-O(2) bond length is 1.28 Å. In the sixth C site, C(3) is bonded in a trigonal planar geometry to one C(1), one C(2), and one C(4) atom. The C(3)-C(4) bond length is 1.39 Å. In the seventh C site, C(4) is bonded in a distorted single-bond geometry to one C(3), one C(6), and one H(2) atom. The C(4)-C(6) bond length is 1.38 Å. The C(4)-H(2) bond length is 0.93 Å. In the eighth C site, C(5) is bonded in a trigonal non-coplanar geometry to one C(6) and three equivalent H(3,4,5) atoms. The C(5)-C(6) bond length is 1.52 Å. All C(5)-H(3,4,5) bond lengths are 0.96 Å. In the ninth C site, C(6) is bonded in a trigonal planar geometry to one C(4), one C(5), and one C(7) atom. The C(6)-C(7) bond length is 1.40 Å. In the tenth C site, C(7) is bonded in a single-bond geometry to one C(6), one C(8), and one H(6) atom. The C(7)-C(8) bond length is 1.38 Å. The C(7)-H(6) bond length is 0.93 Å. In the eleventh C site, C(8) is bonded in a trigonal planar geometry to one C(1), one C(7), and one C(9) atom. The C(8)-C(9) bond length is 1.52 Å. In the twelfth C site, C(9) is bonded in a distorted bent 120 degrees geometry to one C(8), one O(3), and one O(4) atom. The C(9)-O(3) bond length is 1.25 Å. The C(9)-O(4) bond length is 1.26 Å. In the thirteenth C site, C(10) is bonded in a bent 120 degrees geometry to one C(11), one O(5), and one O(6) atom. The C(10)-C(11) bond length is 1.50 Å. The C(10)-O(5) bond length is 1.29 Å. The C(10)-O(6) bond length is 1.24 Å. In the fourteenth C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(13) atom. The C(11)-C(12) bond length is 1.40 Å. In the fifteenth C site, C(12) is bonded in a distorted single-bond geometry to one C(11), one C(14), and one H(7) atom. The C(12)-H(7) bond length is 0.93 Å. There are nine inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(3,4,5) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(6) is bonded in a single-bond geometry to one C(7) atom. In the fifth H site, H(7) is bonded in a single-bond geometry to one C(12) atom. In the sixth H site, H(8) is bonded in a distorted single-bond geometry to one C(15) atom. In the seventh H site, H(9) is bonded in a 1-coordinate geometry to one C(15) atom. In the eighth H site, H(10) is bonded in a 1-coordinate geometry to one C(15) atom. In the ninth H site, H(11) is bonded in a single-bond geometry to one C(13) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one C(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Zn(1), and one C(2) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one C(9) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(9) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Zn(1) and one C(10) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Na(1) and one C(10) atom. Linkers: 4 [CH2].[H].[H].[H].[H].[O]C(=O)c1c[c]cc(C([O])=O)c1 ,8 Cc1cc(C([O])=O)cc(C([O])=O)c1. Metal clusters: 4 O=[C]O[Zn](O[C]=O)O[C]=O.O=[C]O[Zn](O[C]O[Na])O[C]=O. RCSR code: pcu. The MOF has largest included sphere 6.42 A, density 1.40 g/cm3, surface area 4063.68 m2/g, accessible volume 0.31 cm3/g