NaC9(O2Br)3 crystallizes in the cubic I-43d space group. The structure consists of a NaC9(O2Br)3 framework. Na(1) is bonded in an octahedral geometry to three equivalent O(1) and three equivalent O(2) atoms. All Na(1)-O(1) bond lengths are 2.17 Å. All Na(1)-O(2) bond lengths are 2.14 Å. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one Br(1) atom. The C(1)-C(2) bond length is 1.38 Å. The C(1)-C(3) bond length is 1.40 Å. The C(1)-Br(1) bond length is 1.88 Å. In the second C site, C(2) is bonded in a single-bond geometry to one C(1) and one O(1) atom. The C(2)-O(1) bond length is 1.26 Å. In the third C site, C(3) is bonded in a single-bond geometry to one C(1) and one O(2) atom. The C(3)-O(2) bond length is 1.26 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Na(1) and one C(3) atom. Br(1) is bonded in a single-bond geometry to one C(1) atom. Linkers: 24 O=C1[C](Br)C(=O)C(=O)[C](Br)C1=O. Metal clusters: 16 O=[C][C]O[Na].[O][C][C]=O.[O][C][C]=O. RCSR code: srs. The MOF has largest included sphere 6.37 A, density 1.10 g/cm3, surface area 3069.04 m2/g, accessible volume 0.67 cm3/g