Synthesis, Crystal Structure, and Thermal Behaviour of Some New Copper Complexes with tridentate β‐iminoketone ligands

The reaction of Cu(AcO)₂ · H₂O and tridentate β‐iminoketone ligands yielded four new copper complexes: acetato{4‐{[2‐(dimethylamino)ethyl]amino}pent‐3‐en‐2‐onato}copper(II) (1), triacetato{4‐{[3‐(dimethylamino)‐propyl]amino}pent‐3‐en‐2‐onato}dicopper(II) (2), {4‐{[2‐(dimethylamino)ethyl]amino}‐1,1,1‐trifluoropent‐3‐en‐2‐onato}( trifluoroacetato)copper(II) (3), and pentaacetato{4‐{[3‐(dimethylamino)propyl]amino}‐1,1,1‐trifluoropent‐3‐en‐2‐ onato}tricopper(II) (4). All compounds were coloured and air‐stable solids. The crystal structures of 1 and the dioxane adduct of 3, μ‐(1,4‐dioxane)bis{{4‐{[2‐(dimethylamino)ethyl]amino}‐1,1,1‐trifluoropent‐3‐ en‐2‐onato}(trifluoroacetato)copper(II)} (3a), were determined. Complex 1 consists of dimeric units [{Cu(AcO)L}₂] in the solid state (L = β‐iminoketonato ligand). In 3a, two [Cu(CF₃COO)L] are linked via the O‐atoms of the coordinated solvent 1,4‐dioxane. Compound 1 crystallized in the monoclinic space group P2₁/n with a formula unit in a cell having the dimensions a = 11.152(6)Å, b = 10.104(3)Å, c = 11.805(7)Å, and β = 99.02(4)Å, and compound 3a crystallized in the triclinic space group P1 with a formula unit in a cell having the dimensions a = 8.709(3)Å, b = 9.439(4)Å, c = 12.395(3)Å, α = 67.57(3)°, β = 77.01(2)°, and β = 84.17(3)°. Mass spectra (MS), thermal analysis (DTA/TG), and evaporation‐rate measurements are reported for all compounds. The influence of fluorination on the structure and volatility will be discussed.