Co7H21(C14O9)3(CH3CO)6 crystallizes in the trigonal R-3c space group. The structure consists of seventy-two dimethyl ether molecules inside a Co7H21(C14O9)3 framework. In the Co7H21(C14O9)3 framework, there are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(10), one O(11), one O(2), one O(7), and one O(9) atom to form edge-sharing CoO5 square pyramids. The Co(1)-O(10) bond length is 2.21 Å. The Co(1)-O(11) bond length is 2.07 Å. The Co(1)-O(2) bond length is 2.04 Å. The Co(1)-O(7) bond length is 2.07 Å. The Co(1)-O(9) bond length is 2.11 Å. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to one O(1), one O(5), one O(7), one O(8), and two equivalent O(3) atoms. The Co(2)-O(1) bond length is 2.07 Å. The Co(2)-O(5) bond length is 2.11 Å. The Co(2)-O(7) bond length is 2.03 Å. The Co(2)-O(8) bond length is 2.04 Å. There is one shorter (2.14 Å) and one longer (2.51 Å) Co(2)-O(3) bond length. In the third Co site, Co(3) is bonded to three equivalent O(10) and three equivalent O(7) atoms to form edge-sharing CoO6 octahedra. All Co(3)-O(10) bond lengths are 2.13 Å. All Co(3)-O(7) bond lengths are 2.05 Å. There are fourteen inequivalent C sites. In the first C site, C(2) is bonded in a distorted single-bond geometry to one C(11) and one H(9) atom. The C(2)-C(11) bond length is 1.38 Å. The C(2)-H(9) bond length is 0.93 Å. In the second C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(17), one O(10), and one O(9) atom. The C(4)-C(17) bond length is 1.51 Å. The C(4)-O(10) bond length is 1.28 Å. The C(4)-O(9) bond length is 1.25 Å. In the third C site, C(5) is bonded in a distorted single-bond geometry to one C(14) and one H(11) atom. The C(5)-C(14) bond length is 1.40 Å. The C(5)-H(11) bond length is 0.93 Å. In the fourth C site, C(6) is bonded in a distorted single-bond geometry to one C(7) and one H(4) atom. The C(6)-C(7) bond length is 1.43 Å. The C(6)-H(4) bond length is 0.93 Å. In the fifth C site, C(7) is bonded in a trigonal planar geometry to one C(15), one C(6), and one C(9) atom. The C(7)-C(15) bond length is 1.40 Å. The C(7)-C(9) bond length is 1.50 Å. In the sixth C site, C(8) is bonded in a distorted single-bond geometry to one C(17) and one H(12) atom. The C(8)-C(17) bond length is 1.40 Å. The C(8)-H(12) bond length is 0.93 Å. In the seventh C site, C(9) is bonded in a bent 120 degrees geometry to one C(7), one O(3), and one O(8) atom. The C(9)-O(3) bond length is 1.25 Å. The C(9)-O(8) bond length is 1.27 Å. In the eighth C site, C(10) is bonded in a distorted single-bond geometry to one C(11), one C(17), and one H(8) atom. The C(10)-C(11) bond length is 1.40 Å. The C(10)-C(17) bond length is 1.39 Å. The C(10)-H(8) bond length is 0.93 Å. In the ninth C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(2) atom. The C(11)-C(12) bond length is 1.51 Å. In the tenth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(1), and one O(11) atom. The C(12)-O(1) bond length is 1.26 Å. The C(12)-O(11) bond length is 1.27 Å. In the eleventh C site, C(14) is bonded in a trigonal planar geometry to one C(15), one C(16), and one C(5) atom. The C(14)-C(15) bond length is 1.43 Å. The C(14)-C(16) bond length is 1.53 Å. In the twelfth C site, C(15) is bonded in a distorted single-bond geometry to one C(14), one C(7), and one H(5) atom. The C(15)-H(5) bond length is 0.95 Å. In the thirteenth C site, C(16) is bonded in a distorted bent 120 degrees geometry to one C(14), one O(2), and one O(5) atom. The C(16)-O(2) bond length is 1.27 Å. The C(16)-O(5) bond length is 1.27 Å. In the fourteenth C site, C(17) is bonded in a trigonal planar geometry to one C(10), one C(4), and one C(8) atom. There are seven inequivalent H sites. In the first H site, H(12) is bonded in a single-bond geometry to one C(8) atom. In the second H site, H(3) is bonded in a single-bond geometry to one O(7) atom. The H(3)-O(7) bond length is 0.81 Å. In the third H site, H(4) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(5) is bonded in a single-bond geometry to one C(15) atom. In the fifth H site, H(8) is bonded in a single-bond geometry to one C(10) atom. In the sixth H site, H(9) is bonded in a single-bond geometry to one C(2) atom. In the seventh H site, H(11) is bonded in a single-bond geometry to one C(5) atom. There are nine 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(12) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one C(16) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Co(2) and one C(9) atom. In the fourth O site, O(5) is bonded in a bent 120 degrees geometry to one Co(2) and one C(16) atom. In the fifth O site, O(7) is bonded in a distorted single-bond geometry to one Co(1), one Co(2), one Co(3), and one H(3) atom. In the sixth O site, O(8) is bonded in a water-like geometry to one Co(2) and one C(9) atom. In the seventh O site, O(9) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one C(4) atom. In the eighth O site, O(10) is bonded in a 3-coordinate geometry to one Co(1), one Co(3), and one C(4) atom. In the ninth O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Co(1) and one C(12) atom. Linkers: 24 COc1cc(C([O])=O)cc(C([O])=O)c1. Metal clusters: 4 O[Co]123O[C]O[Co](O[C]O[Co]4O[C]O[Co]5O[C]O[Co](O)(O[C]O5)(O[C]O1)O[C]O[Co]1(O)(O[C]O[Co](O[C]O4)O[C]O1)O[C]O2)O[C]O3. RCSR code: pcu. The MOF has largest included sphere 5.84 A, density 1.49 g/cm3, surface area 3385.26 m2/g, accessible volume 0.28 cm3/g