NaC4H6(NO2)3 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one N(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted edge-sharing NaNO5 octahedra. The Na(1)-N(1) bond length is 2.58 Å. The Na(1)-O(2) bond length is 2.48 Å. There is one shorter (2.36 Å) and one longer (2.46 Å) Na(1)-O(3) bond length. There is one shorter (2.38 Å) and one longer (2.48 Å) Na(1)-O(5) bond length. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(2), one C(3), and one N(2) atom. The C(1)-C(2) bond length is 1.48 Å. The C(1)-C(3) bond length is 1.42 Å. The C(1)-N(2) bond length is 1.35 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(4), and one O(6) atom. The C(2)-O(4) bond length is 1.32 Å. The C(2)-O(6) bond length is 1.23 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(1), one C(4), and one N(1) atom. The C(3)-C(4) bond length is 1.49 Å. The C(3)-N(1) bond length is 1.35 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(2) atom. The C(4)-O(1) bond length is 1.29 Å. The C(4)-O(2) bond length is 1.26 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Na(1), one C(3), and one N(3) atom. The N(1)-N(3) bond length is 1.32 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one C(1) and one N(3) atom. The N(2)-N(3) bond length is 1.32 Å. In the third N site, N(3) is bonded in a distorted single-bond geometry to one N(1), one N(2), and one H(6) atom. The N(3)-H(6) bond length is 1.07 Å. There are six inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(5) atom. The H(1)-O(5) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(5) atom. The H(2)-O(5) bond length is 0.99 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(3) atom. The H(3)-O(3) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(3) atom. The H(4)-O(3) bond length is 0.99 Å. In the fifth H site, H(5) is bonded in a linear geometry to one O(1) and one O(4) atom. The H(5)-O(1) bond length is 1.37 Å. The H(5)-O(4) bond length is 1.09 Å. In the sixth H site, H(6) is bonded in a distorted linear geometry to one N(3) and one O(2) atom. The H(6)-O(2) bond length is 1.58 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one C(4) and one H(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one C(4), and one H(6) atom. In the third O site, O(3) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(3), and one H(4) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one C(2) and one H(5) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one C(2) atom. Linkers: 8 O ,2 [O]C(=O)c1n[nH]nc1C(=O)O. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.78 A, density 1.73 g/cm3, surface area 3597.09 m2/g, accessible volume 0.12 cm3/g