NaBC6H4(N2O)6 crystallizes in the trigonal R3c space group. Na(1) is bonded in a 6-coordinate geometry to three equivalent N(2) and three equivalent N(3) atoms. All Na(1)-N(2) bond lengths are 2.62 Å. All Na(1)-N(3) bond lengths are 2.55 Å. B(1) is bonded in a tetrahedral geometry to three equivalent N(1) and one H(2) atom. All B(1)-N(1) bond lengths are 1.55 Å. The B(1)-H(2) bond length is 1.21 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(3), and one H(1) atom. The C(1)-N(1) bond length is 1.36 Å. The C(1)-N(3) bond length is 1.33 Å. The C(1)-H(1) bond length is 1.09 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(2), one N(3), and one N(4) atom. The C(2)-N(2) bond length is 1.33 Å. The C(2)-N(3) bond length is 1.35 Å. The C(2)-N(4) bond length is 1.45 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one B(1), one C(1), and one N(2) atom. The N(1)-N(2) bond length is 1.36 Å. In the second N site, N(2) is bonded in a distorted single-bond geometry to one Na(1), one C(2), and one N(1) atom. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Na(1), one C(1), and one C(2) atom. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(2), one O(1), and one O(2) atom. The N(4)-O(1) bond length is 1.24 Å. The N(4)-O(2) bond length is 1.24 Å. There are two 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 B(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one N(4) atom. In the second O site, O(2) is bonded in a single-bond geometry to one N(4) atom. Linkers: 1 O=N(=O)c1ncn(n1)[BH](n1cnc(n1)N(=O)=O)n1cnc(n1)N(=O)=O ,1 O=N(=O)C1=N[CH]N([N]1)[BH](n1cnc(n1)N(=O)=O)n1cnc(n1)N(=O)=O. Metal clusters: 2 [Na]. The MOF has largest included sphere 1.97 A, density 1.85 g/cm3, surface area 3032.72 m2/g, accessible volume 0.08 cm3/g