Co5C32H22(N2O9)2 crystallizes in the monoclinic C2/c space group. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to one N(2), one N(4), one O(1), one O(17), one O(5), and one O(8) atom to form distorted CoN2O4 octahedra that share  a cornercorner with one Co(2)O5 square pyramid and  a cornercorner with one Co(3)O4 trigonal pyramid. The Co(1)-N(2) bond length is 2.29 Å. The Co(1)-N(4) bond length is 2.17 Å. The Co(1)-O(1) bond length is 2.10 Å. The Co(1)-O(17) bond length is 2.06 Å. The Co(1)-O(5) bond length is 2.09 Å. The Co(1)-O(8) bond length is 2.05 Å. In the second Co site, Co(2) is bonded to one O(17), one O(18), one O(2), one O(3), and one O(6) atom to form CoO5 square pyramids that share  a cornercorner with one Co(1)N2O4 octahedra,  a cornercorner with one Co(5)N2O4 octahedra,  a cornercorner with one Co(4)O4 tetrahedra, and  a cornercorner with one Co(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 41-68°. The Co(2)-O(17) bond length is 2.13 Å. The Co(2)-O(18) bond length is 2.12 Å. The Co(2)-O(2) bond length is 2.09 Å. The Co(2)-O(3) bond length is 2.07 Å. The Co(2)-O(6) bond length is 2.07 Å. In the third Co site, Co(3) is bonded to one O(10), one O(17), one O(4), and one O(7) atom to form distorted CoO4 trigonal pyramids that share  a cornercorner with one Co(1)N2O4 octahedra and  a cornercorner with one Co(2)O5 square pyramid. The corner-sharing octahedral tilt angles are 67°. The Co(3)-O(10) bond length is 2.02 Å. The Co(3)-O(17) bond length is 1.97 Å. The Co(3)-O(4) bond length is 2.06 Å. The Co(3)-O(7) bond length is 1.98 Å. In the fourth Co site, Co(4) is bonded to one O(11), one O(14), one O(16), and one O(18) atom to form CoO4 tetrahedra that share  a cornercorner with one Co(5)N2O4 octahedra and  a cornercorner with one Co(2)O5 square pyramid. The corner-sharing octahedral tilt angles are 77°. The Co(4)-O(11) bond length is 1.99 Å. The Co(4)-O(14) bond length is 2.03 Å. The Co(4)-O(16) bond length is 1.94 Å. The Co(4)-O(18) bond length is 1.96 Å. In the fifth Co site, Co(5) is bonded to one N(1), one N(3), one O(12), one O(13), one O(18), and one O(9) atom to form CoN2O4 octahedra that share  a cornercorner with one Co(2)O5 square pyramid and  a cornercorner with one Co(4)O4 tetrahedra. The Co(5)-N(1) bond length is 2.20 Å. The Co(5)-N(3) bond length is 2.17 Å. The Co(5)-O(12) bond length is 2.08 Å. The Co(5)-O(13) bond length is 2.07 Å. The Co(5)-O(18) bond length is 2.14 Å. The Co(5)-O(9) bond length is 2.06 Å. There are thirty-two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(6), and one C(7) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-C(6) bond length is 1.39 Å. The C(1)-C(7) bond length is 1.51 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one H(11) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-H(11) bond length is 0.95 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(8) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-C(8) bond length is 1.48 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3) and one H(12) atom. The C(4)-H(12) bond length is 0.95 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one N(1) atom. The C(5)-N(1) bond length is 1.44 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(1) and one H(13) atom. The C(6)-H(13) bond length is 0.95 Å. In the seventh C site, C(7) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(1), and one O(2) atom. The C(7)-O(1) bond length is 1.25 Å. The C(7)-O(2) bond length is 1.27 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(3), and one O(4) atom. The C(8)-O(3) bond length is 1.26 Å. The C(8)-O(4) bond length is 1.26 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(14), and one C(15) atom. The C(9)-C(10) bond length is 1.39 Å. The C(9)-C(14) bond length is 1.39 Å. The C(9)-C(15) bond length is 1.51 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(11), one C(9), and one H(14) atom. The C(10)-C(11) bond length is 1.39 Å. The C(10)-H(14) bond length is 0.95 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(16) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-C(16) bond length is 1.51 Å. In the twelfth C site, C(12) is bonded in a distorted single-bond geometry to one C(11), one C(13), and one H(15) atom. The C(12)-C(13) bond length is 1.39 Å. The C(12)-H(15) bond length is 0.95 Å. In the thirteenth C site, C(13) is bonded in a distorted trigonal planar geometry to one C(12), one C(14), and one N(2) atom. The C(13)-C(14) bond length is 1.39 Å. The C(13)-N(2) bond length is 1.44 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(13), one C(9), and one H(16) atom. The C(14)-H(16) bond length is 0.95 Å. In the fifteenth C site, C(15) is bonded in a distorted bent 120 degrees geometry to one C(9), one O(5), and one O(6) atom. The C(15)-O(5) bond length is 1.25 Å. The C(15)-O(6) bond length is 1.25 Å. In the sixteenth C site, C(16) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(7), and one O(8) atom. The C(16)-O(7) bond length is 1.27 Å. The C(16)-O(8) bond length is 1.23 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(18), one C(22), and one C(23) atom. The C(17)-C(18) bond length is 1.39 Å. The C(17)-C(22) bond length is 1.39 Å. The C(17)-C(23) bond length is 1.51 Å. In the eighteenth C site, C(18) is bonded in a distorted single-bond geometry to one C(17), one C(19), and one H(17) atom. The C(18)-C(19) bond length is 1.39 Å. The C(18)-H(17) bond length is 0.95 Å. In the nineteenth C site, C(19) is bonded in a trigonal planar geometry to one C(18), one C(20), and one C(24) atom. The C(19)-C(20) bond length is 1.39 Å. The C(19)-C(24) bond length is 1.50 Å. In the twentieth C site, C(20) is bonded in a distorted single-bond geometry to one C(19) and one H(18) atom. The C(20)-H(18) bond length is 0.95 Å. In the twenty-first C site, C(21) is bonded in a distorted single-bond geometry to one N(3) atom. The C(21)-N(3) bond length is 1.43 Å. In the twenty-second C site, C(22) is bonded in a distorted single-bond geometry to one C(17) and one H(19) atom. The C(22)-H(19) bond length is 0.95 Å. In the twenty-third C site, C(23) is bonded in a distorted bent 120 degrees geometry to one C(17), one O(10), and one O(9) atom. The C(23)-O(10) bond length is 1.26 Å. The C(23)-O(9) bond length is 1.24 Å. In the twenty-fourth C site, C(24) is bonded in a distorted bent 120 degrees geometry to one C(19), one O(11), and one O(12) atom. The C(24)-O(11) bond length is 1.26 Å. The C(24)-O(12) bond length is 1.24 Å. In the twenty-fifth C site, C(25) is bonded in a trigonal planar geometry to one C(26), one C(30), and one C(31) atom. The C(25)-C(26) bond length is 1.39 Å. The C(25)-C(30) bond length is 1.39 Å. The C(25)-C(31) bond length is 1.50 Å. In the twenty-sixth C site, C(26) is bonded in a single-bond geometry to one C(25), one C(27), and one H(20) atom. The C(26)-C(27) bond length is 1.39 Å. The C(26)-H(20) bond length is 0.95 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one C(26), one C(28), and one C(32) atom. The C(27)-C(28) bond length is 1.39 Å. The C(27)-C(32) bond length is 1.48 Å. In the twenty-eighth C site, C(28) is bonded in a distorted single-bond geometry to one C(27) and one H(21) atom. The C(28)-H(21) bond length is 0.95 Å. In the twenty-ninth C site, C(29) is bonded in a distorted single-bond geometry to one N(4) atom. The C(29)-N(4) bond length is 1.43 Å. In the thirtieth C site, C(30) is bonded in a distorted single-bond geometry to one C(25) and one H(22) atom. The C(30)-H(22) bond length is 0.95 Å. In the thirty-first C site, C(31) is bonded in a distorted bent 120 degrees geometry to one C(25), one O(13), and one O(14) atom. The C(31)-O(13) bond length is 1.26 Å. The C(31)-O(14) bond length is 1.26 Å. In the thirty-second C site, C(32) is bonded in a distorted bent 120 degrees geometry to one C(27), one O(15), and one O(16) atom. The C(32)-O(15) bond length is 1.25 Å. The C(32)-O(16) bond length is 1.27 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a distorted water-like geometry to one Co(5), one C(5), one H(3), and one H(4) atom. The N(1)-H(3) bond length is 0.92 Å. The N(1)-H(4) bond length is 0.92 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one Co(1), one C(13), one H(5), and one H(6) atom. The N(2)-H(5) bond length is 0.92 Å. The N(2)-H(6) bond length is 0.92 Å. In the third N site, N(3) is bonded in a distorted water-like geometry to one Co(5); one C(21); and two equivalent H(7,8) atoms. Both N(3)-H(7,8) bond lengths are 0.92 Å. In the fourth N site, N(4) is bonded in a distorted water-like geometry to one Co(1), one C(29), one H(10), and one H(9) atom. The N(4)-H(10) bond length is 0.92 Å. The N(4)-H(9) bond length is 0.92 Å. There are twenty-one inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(17) atom. The H(1)-O(17) bond length is 1.00 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(18) atom. The H(2)-O(18) bond length is 1.00 Å. In the third H site, H(3) is bonded in a single-bond geometry to one N(1) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one N(1) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one N(2) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one N(2) atom. In the seventh H site, H(7,8) is bonded in a single-bond geometry to one N(3) atom. In the eighth H site, H(9) is bonded in a single-bond geometry to one N(4) atom. In the ninth H site, H(10) is bonded in a single-bond geometry to one N(4) atom. In the tenth H site, H(11) is bonded in a single-bond geometry to one C(2) atom. In the eleventh H site, H(12) is bonded in a single-bond geometry to one C(4) atom. In the twelfth H site, H(13) is bonded in a single-bond geometry to one C(6) atom. In the thirteenth H site, H(14) is bonded in a single-bond geometry to one C(10) atom. In the fourteenth H site, H(15) is bonded in a single-bond geometry to one C(12) atom. In the fifteenth H site, H(16) is bonded in a single-bond geometry to one C(14) atom. In the sixteenth H site, H(17) is bonded in a single-bond geometry to one C(18) atom. In the seventeenth H site, H(18) is bonded in a single-bond geometry to one C(20) atom. In the eighteenth H site, H(19) is bonded in a single-bond geometry to one C(22) atom. In the nineteenth H site, H(20) is bonded in a single-bond geometry to one C(26) atom. In the twentieth H site, H(21) is bonded in a single-bond geometry to one C(28) atom. In the twenty-first H site, H(22) is bonded in a single-bond geometry to one C(30) atom. There are eighteen inequivalent O sites. In the first O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Co(5) and one C(23) atom. In the second O site, O(10) is bonded in a 2-coordinate geometry to one Co(3) and one C(23) atom. In the third O site, O(11) is bonded in a bent 120 degrees geometry to one Co(4) and one C(24) atom. In the fourth O site, O(12) is bonded in a bent 150 degrees geometry to one Co(5) and one C(24) atom. In the fifth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Co(5) and one C(31) atom. In the sixth O site, O(14) is bonded in a bent 120 degrees geometry to one Co(4) and one C(31) atom. In the seventh O site, O(15) is bonded in a single-bond geometry to one C(32) atom. In the eighth O site, O(16) is bonded in a water-like geometry to one Co(4) and one C(32) atom. In the ninth O site, O(17) is bonded in a distorted single-bond geometry to one Co(1), one Co(2), one Co(3), and one H(1) atom. In the tenth O site, O(18) is bonded in a distorted single-bond geometry to one Co(2), one Co(4), one Co(5), and one H(2) atom. In the eleventh O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one C(7) atom. In the twelfth O site, O(2) is bonded in a bent 120 degrees geometry to one Co(2) and one C(7) atom. In the thirteenth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Co(2) and one C(8) atom. In the fourteenth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(3) and one C(8) atom. In the fifteenth O site, O(5) is bonded in a bent 150 degrees geometry to one Co(1) and one C(15) atom. In the sixteenth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Co(2) and one C(15) atom. In the seventeenth O site, O(7) is bonded in a bent 120 degrees geometry to one Co(3) and one C(16) atom. In the eighteenth O site, O(8) is bonded in a bent 150 degrees geometry to one Co(1) and one C(16) atom. Linkers: 16 Nc1cc(C([O])=O)cc(C([O])=O)c1. Metal clusters: 2 N[Co]12(N)O[C]O[Co](O[C]O[Co@@](O)(O[C]O[Co]3(N)(N)O[C]O[Co](O)(O[C]=O)O[C]O3)O[C]O1)O[C]O2 ,2 N[Co]12(N)O[C]O[Co](O[C]O[Co@](O)(O[C]O[Co]3(N)(N)O[C]O[Co](O)(O[C]=O)O[C]O3)O[C]O1)O[C]O2. The MOF has largest included sphere 5.83 A, density 1.64 g/cm3, surface area 2961.35 m2/g, accessible volume 0.18 cm3/g