Ce3C36(N3O8)2 crystallizes in the cubic Fm-3 space group. Ce(1) is bonded in a 8-coordinate geometry to four equivalent O(1,2) and four equivalent O(3) atoms. All Ce(1)-O(1,2) bond lengths are 2.39 Å. All Ce(1)-O(3) bond lengths are 2.31 Å. There are eight inequivalent C sites. In the first C site, C(6) is bonded in a distorted trigonal planar geometry to one C(2), one C(6), and one N(1) atom. The C(6)-C(2) bond length is 1.37 Å. The C(6)-C(6) bond length is 1.54 Å. The C(6)-N(1) bond length is 1.37 Å. In the second C site, C(3) is bonded in a bent 120 degrees geometry to one C(5) and one N(1) atom. The C(3)-C(5) bond length is 1.38 Å. The C(3)-N(1) bond length is 1.41 Å. In the third C site, C(1) is bonded in a bent 120 degrees geometry to one C(2) and one C(5) atom. The C(1)-C(2) bond length is 1.41 Å. The C(1)-C(5) bond length is 1.38 Å. In the fourth C site, C(2) is bonded in a bent 120 degrees geometry to one C(1) and one C(6) atom. The C(2)-C(6) bond length is 1.37 Å. In the fifth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(5) and two equivalent O(1,2) atoms. The C(4)-C(5) bond length is 1.50 Å. Both C(4)-O(1,2) bond lengths are 1.25 Å. In the sixth C site, C(5) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(4) atom. In the seventh C site, C(6) is bonded in a distorted trigonal planar geometry to one C(2), one C(6), and one N(1) atom. The C(6)-C(6) bond length is 1.54 Å. The C(6)-N(1) bond length is 1.37 Å. In the eighth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(5) and two equivalent O(1,2) atoms. The C(4)-C(5) bond length is 1.50 Å. Both C(4)-O(1,2) bond lengths are 1.25 Å. N(1) is bonded in a bent 120 degrees geometry to one C(3) and one C(6) atom. There are two inequivalent O sites. In the first O site, O(3) is bonded in a trigonal non-coplanar geometry to three equivalent Ce(1) atoms. In the second O site, O(1,2) is bonded in a distorted bent 120 degrees geometry to one Ce(1) and one C(4) atom. Linkers: 24 [O]C(=O)c1[c][c]c(-c2[c][c]c(C([O])=O)[c]n2)n[c]1. Metal clusters: 2 O=[C]O[Ce]1(O[C]=O)O[Ce]2(O[C]=O)(O[C]=O)O[Ce]345O[C]O[Ce]67(O[C]O[Ce](O[C]O3)(O2)(O4)(O6)O7)(O1)O5.O=[C]O[Ce]O[C]=O.[O][C]=O.[O][C]=O.[O][C]=O ,1 O=[C]O[Ce]1(O[C]=O)O[Ce]234O[C]O[Ce]567(O[C]O[Ce](O[C]O2)(O3)(O[Ce](O[C]=O)(O[C]=O)(O1)O5)(O6)O7)O4.O=[C]O[Ce]O[C]=O.[O][C]=O.[O][C]=O.[O][C]=O ,1 O=[C]O[Ce]12(O[C]=O)O[Ce@]34O[C]O[Ce]567(O[C]O[Ce](O[C]O3)(O1)(O[Ce](O[C]=O)(O[C]=O)(O2)O5)(O6)O7)O4.O=[C]O[Ce]O[C]=O.[O][C]=O.[O][C]=O.[O][C]=O. RCSR code: fcu. The MOF has largest included sphere 13.72 A, density 0.78 g/cm3, surface area 3083.21 m2/g, accessible volume 0.89 cm3/g