Na2CuC12H20(N2O3)6 crystallizes in the triclinic P-1 space group. Na(1) is bonded to one O(2), one O(9), two equivalent O(5), and two equivalent O(8) atoms to form edge-sharing NaO6 octahedra. The Na(1)-O(2) bond length is 2.30 Å. The Na(1)-O(9) bond length is 2.51 Å. There is one shorter (2.31 Å) and one longer (2.60 Å) Na(1)-O(5) bond length. There is one shorter (2.43 Å) and one longer (2.48 Å) Na(1)-O(8) bond length. Cu(1) is bonded in a square co-planar geometry to two equivalent N(1) and two equivalent O(7) atoms. Both Cu(1)-N(1) bond lengths are 1.96 Å. Both Cu(1)-O(7) bond lengths are 1.96 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(2), and one O(1) atom. The C(1)-N(1) bond length is 1.36 Å. The C(1)-N(2) bond length is 1.38 Å. The C(1)-O(1) bond length is 1.25 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(2), one N(3), and one O(2) atom. The C(2)-N(2) bond length is 1.38 Å. The C(2)-N(3) bond length is 1.38 Å. The C(2)-O(2) bond length is 1.24 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one N(1), one N(3), and one O(3) atom. The C(3)-N(1) bond length is 1.36 Å. The C(3)-N(3) bond length is 1.38 Å. The C(3)-O(3) bond length is 1.25 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one N(4), one N(5), and one O(4) atom. The C(4)-N(4) bond length is 1.35 Å. The C(4)-N(5) bond length is 1.39 Å. The C(4)-O(4) bond length is 1.26 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one N(5), one N(6), and one O(5) atom. The C(5)-N(5) bond length is 1.37 Å. The C(5)-N(6) bond length is 1.37 Å. The C(5)-O(5) bond length is 1.24 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one N(4), one N(6), and one O(6) atom. The C(6)-N(4) bond length is 1.35 Å. The C(6)-N(6) bond length is 1.39 Å. The C(6)-O(6) bond length is 1.26 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(3) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one C(1), one C(2), and one H(1) atom. The N(2)-H(1) bond length is 1.05 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one C(2), one C(3), and one H(2) atom. The N(3)-H(2) bond length is 1.05 Å. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(4), one C(6), and one H(6) atom. The N(4)-H(6) bond length is 1.60 Å. In the fifth N site, N(5) is bonded in a trigonal planar geometry to one C(4), one C(5), and one H(3) atom. The N(5)-H(3) bond length is 1.05 Å. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one C(5), one C(6), and one H(4) atom. The N(6)-H(4) bond length is 1.05 Å. There are ten inequivalent H sites. In the first H site, H(1) is bonded in a distorted single-bond geometry to one N(2) and one O(4) atom. The H(1)-O(4) bond length is 1.68 Å. In the second H site, H(2) is bonded in a distorted linear geometry to one N(3) and one O(6) atom. The H(2)-O(6) bond length is 1.67 Å. In the third H site, H(3) is bonded in a distorted single-bond geometry to one N(5) and one O(1) atom. The H(3)-O(1) bond length is 1.68 Å. In the fourth H site, H(4) is bonded in a distorted single-bond geometry to one N(6) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(7) atom. The H(5)-O(7) bond length is 1.01 Å. In the sixth H site, H(6) is bonded in a distorted linear geometry to one N(4) and one O(7) atom. The H(6)-O(7) bond length is 1.03 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(8) atom. The H(7)-O(8) bond length is 0.98 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(8) atom. The H(8)-O(8) bond length is 0.98 Å. In the ninth H site, H(9) is bonded in a single-bond geometry to one O(9) atom. The H(9)-O(9) bond length is 0.98 Å. In the tenth H site, H(10) is bonded in a single-bond geometry to one O(9) atom. The H(10)-O(9) bond length is 0.99 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one C(1) and one H(3) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one C(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one C(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one C(4) and one H(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(5) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one C(6) and one H(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Cu(1), one H(5), and one H(6) atom. In the eighth O site, O(8) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(7), and one H(8) atom. In the ninth O site, O(9) is bonded in a distorted water-like geometry to one Na(1), one H(10), and one H(9) atom. Linkers: 2 O=C1[N]C(=O)NC(=O)N1. Metal clusters: 2 [Na] ,1 O.O.[Cu]. The MOF has largest included sphere 1.74 A, density 1.98 g/cm3, surface area 3241.62 m2/g, accessible volume 0.06 cm3/g