CaCu6C21H12(N2O7)3(CH2)3(C2H5S)6 crystallizes in the hexagonal P6_3 space group. The structure consists of six 02329_fluka molecules and six methylsulfanylmethane molecules inside a CaCu6C21H12(N2O7)3 framework. In the CaCu6C21H12(N2O7)3 framework, Ca(1) is bonded in a 9-coordinate geometry to three equivalent O(1), three equivalent O(2), and three equivalent O(5) atoms. All Ca(1)-O(1) bond lengths are 2.60 Å. All Ca(1)-O(2) bond lengths are 2.51 Å. All Ca(1)-O(5) bond lengths are 2.44 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one N(1), one O(1), one O(2), one O(3), and one O(4) atom to form corner-sharing CuNO4 square pyramids. The Cu(1)-N(1) bond length is 1.86 Å. The Cu(1)-O(1) bond length is 1.98 Å. The Cu(1)-O(2) bond length is 1.98 Å. The Cu(1)-O(3) bond length is 1.97 Å. The Cu(1)-O(4) bond length is 2.25 Å. In the second Cu site, Cu(2) is bonded to one N(2), one O(1), one O(5), one O(6), and one O(7) atom to form distorted corner-sharing CuNO4 square pyramids. The Cu(2)-N(2) bond length is 1.91 Å. The Cu(2)-O(1) bond length is 1.84 Å. The Cu(2)-O(5) bond length is 2.01 Å. The Cu(2)-O(6) bond length is 2.09 Å. The Cu(2)-O(7) bond length is 2.29 Å. There are seven inequivalent C sites. In the first C site, C(1) is bonded in a 2-coordinate geometry to one C(2), one O(2), and one O(4) atom. The C(1)-C(2) bond length is 1.63 Å. The C(1)-O(2) bond length is 1.23 Å. The C(1)-O(4) bond length is 1.30 Å. In the second C site, C(2) is bonded in a 4-coordinate geometry to one C(1), one C(7), one N(1), and one H(1) atom. The C(2)-C(7) bond length is 1.53 Å. The C(2)-N(1) bond length is 1.60 Å. The C(2)-H(1) bond length is 1.00 Å. In the third C site, C(3) is bonded in a 2-coordinate geometry to one N(2) and one O(3) atom. The C(3)-N(2) bond length is 1.34 Å. The C(3)-O(3) bond length is 1.27 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one N(1) and one O(6) atom. The C(4)-N(1) bond length is 1.30 Å. The C(4)-O(6) bond length is 1.32 Å. In the fifth C site, C(5) is bonded in a distorted bent 120 degrees geometry to one O(5) and one O(7) atom. The C(5)-O(5) bond length is 1.36 Å. The C(5)-O(7) bond length is 1.19 Å. In the sixth C site, C(6) is bonded in a 2-coordinate geometry to one N(2) and one H(2) atom. The C(6)-N(2) bond length is 1.36 Å. The C(6)-H(2) bond length is 1.00 Å. In the seventh C site, C(7) is bonded in a water-like geometry to one C(2), one H(3), and one H(4) atom. The C(7)-H(3) bond length is 0.99 Å. The C(7)-H(4) bond length is 0.99 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(2), and one C(4) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(2), one C(3), and one C(6) atom. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(7) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(7) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one Cu(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(1), and one C(1) atom. In the third O site, O(3) is bonded in a water-like geometry to one Cu(1) and one C(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(1), one Cu(2), and one C(5) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one Cu(2) and one C(4) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Cu(2) and one C(5) atom. Linkers: 6 CSCC[C@H]([N]C(=O)C(=O)[N][C@H](CCSC)C([O])=O)C([O])=O. Metal clusters: 2 [Ca] ,12 [Cu]. The MOF has largest included sphere 5.16 A, density 1.44 g/cm3, surface area 3533.34 m2/g, accessible volume 0.29 cm3/g