NaBa2Co2C20N4O22Cl crystallizes in the monoclinic Cc space group. Na(1) is bonded in a distorted trigonal non-coplanar geometry to one O(11), one O(20), and one O(3) atom. The Na(1)-O(11) bond length is 2.29 Å. The Na(1)-O(20) bond length is 2.59 Å. The Na(1)-O(3) bond length is 2.35 Å. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(1), one O(13), one O(14), one O(17), one O(2), one O(21), one O(22), one O(5), and one O(7) atom. The Ba(1)-O(1) bond length is 2.92 Å. The Ba(1)-O(13) bond length is 3.08 Å. The Ba(1)-O(14) bond length is 2.83 Å. The Ba(1)-O(17) bond length is 2.81 Å. The Ba(1)-O(2) bond length is 2.99 Å. The Ba(1)-O(21) bond length is 2.95 Å. The Ba(1)-O(22) bond length is 2.88 Å. The Ba(1)-O(5) bond length is 2.78 Å. The Ba(1)-O(7) bond length is 2.83 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one O(10), one O(13), one O(15), one O(21), one O(22), one O(5), one O(6), and one O(9) atom. The Ba(2)-O(10) bond length is 2.97 Å. The Ba(2)-O(13) bond length is 2.80 Å. The Ba(2)-O(15) bond length is 2.79 Å. The Ba(2)-O(21) bond length is 2.87 Å. The Ba(2)-O(22) bond length is 2.99 Å. The Ba(2)-O(5) bond length is 3.09 Å. The Ba(2)-O(6) bond length is 2.84 Å. The Ba(2)-O(9) bond length is 2.90 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in an octahedral geometry to one N(1), one N(2), one O(2), one O(4), one O(6), and one O(8) atom. The Co(1)-N(1) bond length is 1.93 Å. The Co(1)-N(2) bond length is 1.93 Å. The Co(1)-O(2) bond length is 1.93 Å. The Co(1)-O(4) bond length is 1.89 Å. The Co(1)-O(6) bond length is 1.91 Å. The Co(1)-O(8) bond length is 1.90 Å. In the second Co site, Co(2) is bonded in an octahedral geometry to one N(3), one N(4), one O(10), one O(12), one O(14), and one O(16) atom. The Co(2)-N(3) bond length is 1.93 Å. The Co(2)-N(4) bond length is 1.93 Å. The Co(2)-O(10) bond length is 1.92 Å. The Co(2)-O(12) bond length is 1.89 Å. The Co(2)-O(14) bond length is 1.93 Å. The Co(2)-O(16) bond length is 1.90 Å. There are twenty inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one N(1) atom. The C(1)-N(1) bond length is 1.50 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one N(2) atom. The C(2)-N(2) bond length is 1.52 Å. In the third C site, C(3) is bonded in a distorted water-like geometry to one C(4) and one N(1) atom. The C(3)-C(4) bond length is 1.53 Å. The C(3)-N(1) bond length is 1.50 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(2) atom. The C(4)-O(1) bond length is 1.24 Å. The C(4)-O(2) bond length is 1.30 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(6) and one N(1) atom. The C(5)-C(6) bond length is 1.51 Å. The C(5)-N(1) bond length is 1.51 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(3), and one O(4) atom. The C(6)-O(3) bond length is 1.22 Å. The C(6)-O(4) bond length is 1.31 Å. In the seventh C site, C(7) is bonded in a distorted water-like geometry to one C(8) and one N(2) atom. The C(7)-C(8) bond length is 1.54 Å. The C(7)-N(2) bond length is 1.51 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(7), one O(5), and one O(6) atom. The C(8)-O(5) bond length is 1.22 Å. The C(8)-O(6) bond length is 1.32 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(10) and one N(2) atom. The C(9)-C(10) bond length is 1.51 Å. The C(9)-N(2) bond length is 1.50 Å. In the tenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one C(9), one O(7), and one O(8) atom. The C(10)-O(7) bond length is 1.23 Å. The C(10)-O(8) bond length is 1.30 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one N(3) atom. The C(11)-N(3) bond length is 1.51 Å. In the twelfth C site, C(12) is bonded in a distorted single-bond geometry to one N(4) atom. The C(12)-N(4) bond length is 1.51 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one N(3) atom. The C(13)-N(3) bond length is 1.49 Å. In the fourteenth C site, C(14) is bonded in a distorted bent 120 degrees geometry to one O(10) and one O(9) atom. The C(14)-O(10) bond length is 1.29 Å. The C(14)-O(9) bond length is 1.24 Å. In the fifteenth C site, C(15) is bonded in a distorted single-bond geometry to one N(3) atom. The C(15)-N(3) bond length is 1.49 Å. In the sixteenth C site, C(16) is bonded in a distorted bent 120 degrees geometry to one O(11) and one O(12) atom. The C(16)-O(11) bond length is 1.24 Å. The C(16)-O(12) bond length is 1.30 Å. In the seventeenth C site, C(17) is bonded in a distorted single-bond geometry to one N(4) atom. The C(17)-N(4) bond length is 1.49 Å. In the eighteenth C site, C(18) is bonded in a distorted bent 120 degrees geometry to one O(13) and one O(14) atom. The C(18)-O(13) bond length is 1.23 Å. The C(18)-O(14) bond length is 1.30 Å. In the nineteenth C site, C(19) is bonded in a distorted single-bond geometry to one N(4) atom. The C(19)-N(4) bond length is 1.50 Å. In the twentieth C site, C(20) is bonded in a distorted bent 120 degrees geometry to one O(15) and one O(16) atom. The C(20)-O(15) bond length is 1.23 Å. The C(20)-O(16) bond length is 1.30 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded to one Co(1), one C(1), one C(3), and one C(5) atom to form corner-sharing NCoC3 tetrahedra. In the second N site, N(2) is bonded to one Co(1), one C(2), one C(7), and one C(9) atom to form corner-sharing NCoC3 tetrahedra. In the third N site, N(3) is bonded to one Co(2), one C(11), one C(13), and one C(15) atom to form corner-sharing NCoC3 tetrahedra. In the fourth N site, N(4) is bonded to one Co(2), one C(12), one C(17), and one C(19) atom to form corner-sharing NCoC3 tetrahedra. There are twenty-two inequivalent O sites. In the first O site, O(9) is bonded in a distorted single-bond geometry to one Ba(2) and one C(14) atom. In the second O site, O(10) is bonded in a distorted water-like geometry to one Ba(2), one Co(2), and one C(14) atom. In the third O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one C(16) atom. In the fourth O site, O(12) is bonded in a bent 120 degrees geometry to one Co(2) and one C(16) atom. In the fifth O site, O(13) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one C(18) atom. In the sixth O site, O(14) is bonded in a 2-coordinate geometry to one Ba(1), one Co(2), and one C(18) atom. In the seventh O site, O(15) is bonded in a distorted single-bond geometry to one Ba(2) and one C(20) atom. In the eighth O site, O(16) is bonded in a bent 120 degrees geometry to one Co(2) and one C(20) atom. In the ninth O site, O(17) is bonded in a distorted bent 150 degrees geometry to one Ba(1) and one Cl(1) atom. The O(17)-Cl(1) bond length is 1.42 Å. In the tenth O site, O(18) is bonded in a single-bond geometry to one Cl(1) atom. The O(18)-Cl(1) bond length is 1.41 Å. In the eleventh O site, O(19) is bonded in a single-bond geometry to one Cl(1) atom. The O(19)-Cl(1) bond length is 1.45 Å. In the twelfth O site, O(20) is bonded in a bent 120 degrees geometry to one Na(1) and one Cl(1) atom. The O(20)-Cl(1) bond length is 1.46 Å. In the thirteenth O site, O(21) is bonded in a bent 120 degrees geometry to one Ba(1) and one Ba(2) atom. In the fourteenth O site, O(22) is bonded in a bent 120 degrees geometry to one Ba(1) and one Ba(2) atom. In the fifteenth O site, O(1) is bonded in a single-bond geometry to one Ba(1) and one C(4) atom. In the sixteenth O site, O(2) is bonded in a distorted water-like geometry to one Ba(1), one Co(1), and one C(4) atom. In the seventeenth O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one C(6) atom. In the eighteenth O site, O(4) is bonded in a bent 120 degrees geometry to one Co(1) and one C(6) atom. In the nineteenth O site, O(5) is bonded in a distorted single-bond geometry to one Ba(1), one Ba(2), and one C(8) atom. In the twentieth O site, O(6) is bonded in a 2-coordinate geometry to one Ba(2), one Co(1), and one C(8) atom. In the twenty-first O site, O(7) is bonded in a distorted single-bond geometry to one Ba(1) and one C(10) atom. In the twenty-second O site, O(8) is bonded in a bent 120 degrees geometry to one Co(1) and one C(10) atom. Cl(1) is bonded in a tetrahedral geometry to one O(17), one O(18), one O(19), and one O(20) atom. Linkers: 8 [O]C(=O)[C]N([C][C]N([C]C([O])=O)[C]C([O])=O)[C]C([O])=O. Metal clusters: 8 [Ba] ,4 [Na] ,8 [Co]. The MOF has largest included sphere 4.55 A, density 1.66 g/cm3, surface area 3327.63 m2/g, accessible volume 0.22 cm3/g