Cu3H22(C19O8)2 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Cu(1)-O(1) bond lengths are 1.95 Å. Both Cu(1)-O(2) bond lengths are 1.96 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to four equivalent O(3) atoms. All Cu(2)-O(3) bond lengths are 1.87 Å. There are twelve inequivalent C sites. In the first C site, C(1) is bonded in a bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.47 Å. The C(1)-O(1) bond length is 1.24 Å. The C(1)-O(2) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(8) atom. The C(2)-C(3) bond length is 1.36 Å. The C(2)-C(8) bond length is 1.38 Å. In the third C site, C(4) is bonded in a 2-coordinate geometry to one C(10), one C(6), and one H(2) atom. The C(4)-C(10) bond length is 1.42 Å. The C(4)-C(6) bond length is 1.16 Å. The C(4)-H(2) bond length is 0.93 Å. In the fourth C site, C(5) is bonded in a 2-coordinate geometry to one C(11), one C(7), and one H(3) atom. The C(5)-C(11) bond length is 1.36 Å. The C(5)-C(7) bond length is 1.12 Å. The C(5)-H(3) bond length is 0.93 Å. In the fifth C site, C(6) is bonded in a 4-coordinate geometry to one C(10), one C(4), one C(7), and one H(4) atom. The C(6)-C(10) bond length is 1.32 Å. The C(6)-C(7) bond length is 1.36 Å. The C(6)-H(4) bond length is 0.93 Å. In the sixth C site, C(7) is bonded in a 4-coordinate geometry to one C(11), one C(5), one C(6), and one H(5) atom. The C(7)-C(11) bond length is 1.35 Å. The C(7)-H(5) bond length is 0.93 Å. In the seventh C site, C(3) is bonded in a single-bond geometry to one C(2), one C(9), and one H(1) atom. The C(3)-C(9) bond length is 1.39 Å. The C(3)-H(1) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to two equivalent C(2) and one H(6) atom. The C(8)-H(6) bond length is 0.93 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10) and two equivalent C(3) atoms. The C(9)-C(10) bond length is 1.51 Å. In the tenth C site, C(10) is bonded in a 5-coordinate geometry to one C(9), two equivalent C(4), and two equivalent C(6) atoms. In the eleventh C site, C(11) is bonded in a 5-coordinate geometry to one C(12), two equivalent C(5), and two equivalent C(7) atoms. The C(11)-C(12) bond length is 1.47 Å. In the twelfth C site, C(12) is bonded in a 5-coordinate geometry to one C(11), two equivalent O(3), and two equivalent O(4) atoms. Both C(12)-O(3) bond lengths are 1.23 Å. Both C(12)-O(4) bond lengths are 1.27 Å. There are six inequivalent H sites. In the first H site, H(6) is bonded in a single-bond geometry to one C(8) atom. In the second H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(2) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(3) is bonded in a single-bond geometry to one C(5) atom. In the fifth H site, H(4) is bonded in a single-bond geometry to one C(6) atom. In the sixth H site, H(5) is bonded in a single-bond geometry to one C(7) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Cu(1) and one C(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Cu(2), one C(12), and one O(4) atom. The O(3)-O(4) bond length is 0.83 Å. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one C(12) and one O(3) atom. Linkers: 10 [C@H]12[C@@H]3[C@@H]4[C@H]1C41[C@@H]4[C@H]5[C@@H]([C@@H]41)C235.[O]C(=O)c1c[c]cc(C([O])=O)c1.[O]O[C]O[O] ,2 [C@H]12[C@@H]3[C@@H]4[C@H]1C41[C@H]4[C@@H]5[C@H]([C@H]41)C235.[O]C(=O)c1c[c]cc(C([O])=O)c1.[O]O[C]O[O]. Metal clusters: 6 [C]1O[Cu]234O[C]O[Cu]2(O1)(O[C]O3)O[C]O4 ,6 [O]O[Cu](O[O])(O[O])O[O]. RCSR code: kgm. The MOF has largest included sphere 13.77 A, density 0.78 g/cm3, surface area 3182.73 m2/g, accessible volume 0.98 cm3/g