Ca6C37H40O21(CH)8(CH2)4 crystallizes in the tetragonal I4_1/amd space group. The structure consists of sixty-four 02329_fluka molecules and thirty-two 02329_fluka molecules inside a Ca6C37H40O21 framework. In the Ca6C37H40O21 framework, there are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one O(5), two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. The Ca(1)-O(5) bond length is 2.41 Å. Both Ca(1)-O(1) bond lengths are 2.60 Å. Both Ca(1)-O(2) bond lengths are 2.48 Å. Both Ca(1)-O(3) bond lengths are 2.37 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. Both Ca(2)-O(1) bond lengths are 2.29 Å. Both Ca(2)-O(3) bond lengths are 2.59 Å. Both Ca(2)-O(4) bond lengths are 2.49 Å. In the third Ca site, Ca(3) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(7) atoms to form distorted edge-sharing CaO6 octahedra. Both Ca(3)-O(2) bond lengths are 2.19 Å. Both Ca(3)-O(5) bond lengths are 2.36 Å. Both Ca(3)-O(7) bond lengths are 2.30 Å. There are ten inequivalent C sites. In the first C site, C(13) is bonded in a trigonal planar geometry to one O(6) and two equivalent O(7) atoms. The C(13)-O(6) bond length is 1.20 Å. Both C(13)-O(7) bond lengths are 1.20 Å. In the second C site, C(1) is bonded to one C(11), one C(2), one C(6), and one C(7) atom to form corner-sharing CC4 tetrahedra. The C(1)-C(11) bond length is 1.51 Å. The C(1)-C(2) bond length is 1.53 Å. The C(1)-C(6) bond length is 1.54 Å. The C(1)-C(7) bond length is 1.55 Å. In the third C site, C(2) is bonded in a water-like geometry to one C(1); one C(3); and two equivalent H(1,2) atoms. The C(2)-C(3) bond length is 1.53 Å. Both C(2)-H(1,2) bond lengths are 0.97 Å. In the fourth C site, C(3) is bonded to one C(12), one C(2), one C(4), and one C(8) atom to form corner-sharing CC4 tetrahedra. The C(3)-C(12) bond length is 1.51 Å. The C(3)-C(4) bond length is 1.55 Å. The C(3)-C(8) bond length is 1.54 Å. In the fifth C site, C(4) is bonded in a water-like geometry to one C(3) and two equivalent H(3,4,11) atoms. Both C(4)-H(3,4,11) bond lengths are 0.97 Å. In the sixth C site, C(6) is bonded in a water-like geometry to one C(1) and two equivalent H(6,7,8) atoms. Both C(6)-H(6,7,8) bond lengths are 0.97 Å. In the seventh C site, C(7) is bonded in a water-like geometry to one C(1); one H(6,7,8); and one H(9) atom. The C(7)-H(6,7,8) bond length is 0.97 Å. The C(7)-H(9) bond length is 0.97 Å. In the eighth C site, C(8) is bonded in a water-like geometry to one C(3); one H(10); and one H(3,4,11) atom. The C(8)-H(10) bond length is 0.97 Å. The C(8)-H(3,4,11) bond length is 0.97 Å. In the ninth C site, C(11) is bonded in a distorted water-like geometry to one C(1), one O(1), and one O(2) atom. The C(11)-O(1) bond length is 1.35 Å. The C(11)-O(2) bond length is 1.26 Å. In the tenth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(3), and one O(4) atom. The C(12)-O(3) bond length is 1.25 Å. The C(12)-O(4) bond length is 1.33 Å. There are five inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(3,4,11) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(6,7,8) is bonded in a single-bond geometry to one C(6) atom. In the fourth H site, H(9) is bonded in a single-bond geometry to one C(7) atom. In the fifth H site, H(10) is bonded in a single-bond geometry to one C(8) atom. There are seven inequivalent O sites. In the first O site, O(4) is bonded in a distorted single-bond geometry to one Ca(2) and one C(12) atom. In the second O site, O(5) is bonded in a trigonal non-coplanar geometry to one Ca(1) and two equivalent Ca(3) atoms. In the third O site, O(6) is bonded in a single-bond geometry to one C(13) atom. In the fourth O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Ca(3) and one C(13) atom. In the fifth O site, O(1) is bonded in a distorted T-shaped geometry to one Ca(1), one Ca(2), and one C(11) atom. In the sixth O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(3), and one C(11) atom. In the seventh O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one Ca(2), and one C(12) atom. Linkers: 16 [O]C(=O)[C@]12C[C@H]3C[C@H](C[C@](C([O])=O)(C3)C1)C2. Metal clusters: 24 [Ca]. The MOF has largest included sphere 7.32 A, density 1.21 g/cm3, surface area 3907.99 m2/g, accessible volume 0.31 cm3/g