Co-crystal structure, Hirshfeld surface analysis and DFT studies of 3,4-ethyl-ene-dioxy-thio-phene solvated bis-[1,3-bis-(penta-fluoro-phen-yl)propane-1,3-dionato]copper(II).

The title complex, Cu(L)2 or [Cu(C15HF10O2)2], comprised of one copper ion and two fully fluorinated ligands (L -), was crystallized with 3,4-ethyl-ene-dioxy-thio-phene (EDOT, C6H6O2S) as a guest mol-ecule to give in a di-chloro-methane solution a unique co-crystal, Cu(L)2·3C6H6O2S. In the crystal, the oxygen of one guest mol-ecule, EDOT-1, is coordinated to the metal to give an alternate linear arrangement, and the π-planes of the others, EDOT-2 and EDOT-3, inter-act weakly with the penta-fluoro-phenyl groups of the complex through arene-perfluoro-arene inter-actions. Head-to-tail columnar and head-to-head dimeric arrangements are observed for EDOT-2 and EDOT-3, respectively, in the crystal. The Hirshfeld surface analysis indicated that the most important contributions for the crystal packing are from the F⋯F (20.4%), F⋯H/H⋯F (24.5%) and F⋯C/C⋯F (9.6%) inter-actions. The density functional theory (DFT) optimized structure at the ωB97X-D 6-31G* level was compared with the experimentally determined mol-ecular structure in the solid state.

Enhanced and Heteromolecular Guest Encapsulation in Nonporous Crystals of a Perfluorinated Triketonato Dinuclear Copper Complex.

The flexible host framework of a perfluorinated mononuclear copper complex, [Cu(L1 )2 ] (1, HL1 =3-hydroxy-1,3-bis(pentafluorophenyl)-2-propen-1-one), with a CuO4 core reversibly encapsulated several organic guest molecules through electrostatic interactions in its crystals. Hence, the corresponding dinuclear complex, [Cu2 (L2 )2 ] (2, H2 L2 =1,5-dihydroxy-1,5-bis(pentafluorophenyl)-1,4-pentadien-3-one), was prepared to enhance guest recognition and the ability to separate molecular mixtures. Complex 2 comprises a Cu2 O6 core and four pentafluorophenyl groups. In crystal 2, cavities are formed on the axial sites of the metal core that are surrounded by pentafluorophenyl groups. The crystal of 2 encapsulates various guest molecules, that is, benzene (3), toluene (4), xylene (5), mesitylene (6), durene (7), and anisole (8). X-ray crystallographic and thermogravimetric (TG) studies show that three guest molecules are present in the crystal cavities. The number of guest molecules found in complex 2 was higher than that in complex 1, for example, (2)3 ⋅(6)10 >1⋅(6)2 , (2)2 ⋅(7)7 >1⋅7, or 2⋅(8)3 >1⋅(8)2 . Naphthalene (9), was encapsulated in 2 to give 2⋅(9)3 , but not in 1. In the crystal of complex 2, heteromolecular guest encapsulation was confirmed, designated as 2⋅(3)2 ⋅9. TG analysis indicates that the thermal stability of the guest-included crystals of 2 is higher than that of 1.