Synthesis and Structure of Complexes Formed in the CuCl2–Cu–N-allylquinolinium Chloride System

Abstract

The crystals of [C₉H₇N(C₃H₅)]₂Cu^IICl₄(IV) were obtained through ac electrochemical synthesis using CuCl₂· 2H₂O, N-allylquinolinium chloride, and copper electrodes in an ethanol-benzene medium. These crystals transformed with time into crystals of the [C₉H₇N(C₃H₅)][Cu^IICl₃(C₉H₇N)] complex (V). When tin(II) chloride was added to the initial reagents, the [C₉H₇N(C₃H₅)]Cu^I ₂Cl₃complex (VI) was obtained. The X-ray diffraction analysis (DARCh-1 autodiffractometer, MoK _αradiation, Zr filter) indicated that complexes IVand Vcrystallize in the triclinic system: space group P $\overline {\text{1}}$; for IV, a= 12.817(4), b= 10.435(3), c= 9.606(3) Å, α = 97.94(2)°, β = 107.28(2)°, γ = 95.99(2)°, V= 1200.6(6) ų, Z= 2; for V, a= 16.992(5), b= 8.243(2), c= 7.345(3) Å, α = 91.89(3)°, β = 91.19(3)°, γ = 88.18(3)°, V= 1027.5(6) ų, Z= 2. Crystals VIare monoclinic, space group P2₁/n, a= 13.578(5), b= 15.079(4), c= 6.953(4) Å, β = 105.08(4)°, V= 1370.6(10) ų, Z= 4. Structures IV–VIconsist of N-allylquinolinium cations and different anions: isolated [CuCl₄]^2–tetrahedrons (IV), [C₉H₇NCuCl₃]^–tetrahedrons (V) containing a quinoline molecule, and a polymer chain |[Cu^I ₄Cl₆]^2–} _n (VI) in which two independent metal atoms have trigonal-pyramidal and planar-trigonal environments. The C=C bond of the allyl group is not involved in cooordination with the Cu(I) atom.