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)

Abstract

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.

Keywords: 3,4-ethyl­ene­dioxy­thio­phene; EDOT; Hirshfeld surface analysis; co-crystal; crystal structure.