Li3Co8C48(N3O4)12 crystallizes in the trigonal R-3c space group. Li(1) is bonded in a tetrahedral geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(1)-O(2) bond lengths are 1.91 Å. Both Li(1)-O(3) bond lengths are 1.91 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in an octahedral geometry to one N(3), one N(4), one N(6), one O(4), one O(5), and one O(8) atom. The Co(1)-N(3) bond length is 2.03 Å. The Co(1)-N(4) bond length is 2.03 Å. The Co(1)-N(6) bond length is 2.02 Å. The Co(1)-O(4) bond length is 2.02 Å. The Co(1)-O(5) bond length is 2.00 Å. The Co(1)-O(8) bond length is 2.02 Å. In the second Co site, Co(2) is bonded in an octahedral geometry to three equivalent N(1) and three equivalent O(1) atoms. All Co(2)-N(1) bond lengths are 2.03 Å. All Co(2)-O(1) bond lengths are 2.01 Å. There are eight inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(2) bond length is 1.23 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one N(1) atom. The C(2)-N(1) bond length is 1.33 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one N(3) atom. The C(3)-N(3) bond length is 1.35 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(4)-O(3) bond length is 1.25 Å. The C(4)-O(4) bond length is 1.26 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(6) atom. The C(5)-O(5) bond length is 1.26 Å. The C(5)-O(6) bond length is 1.22 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one N(4) atom. The C(6)-N(4) bond length is 1.38 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one N(6) atom. The C(7)-N(6) bond length is 1.36 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one O(7) and one O(8) atom. The C(8)-O(7) bond length is 1.22 Å. The C(8)-O(8) bond length is 1.27 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Co(2), one C(2), and one N(2) atom. The N(1)-N(2) bond length is 1.33 Å. In the second N site, N(2) is bonded in a water-like geometry to one N(1) and one N(3) atom. The N(2)-N(3) bond length is 1.31 Å. In the third N site, N(3) is bonded in a 3-coordinate geometry to one Co(1), one C(3), and one N(2) atom. In the fourth N site, N(4) is bonded in a 3-coordinate geometry to one Co(1), one C(6), and one N(5) atom. The N(4)-N(5) bond length is 1.31 Å. In the fifth N site, N(5) is bonded in a water-like geometry to one N(4) and one N(6) atom. The N(5)-N(6) bond length is 1.30 Å. In the sixth N site, N(6) is bonded in a 3-coordinate geometry to one Co(1), one C(7), and one N(5) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Co(2) and one C(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one C(4) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(1) and one C(4) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Co(1) and one C(5) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one C(5) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one C(8) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Co(1) and one C(8) atom. Linkers: 28 [O]C(=O)C1=C(C([O])=O)N=N[N]1 ,26 [O]C(=O)[C]1N=NN=C1C([O])=O ,17 [O]C(=O)C1=N[N]N=C1C([O])=O. Metal clusters: 18 [Li] ,48 [Co]. The MOF has largest included sphere 8.23 A, density 1.13 g/cm3, surface area 3503.83 m2/g, accessible volume 0.52 cm3/g