Polymorphism of Copper(I) Halide π-Complexes: Synthesis and Structure of a New Modification of [Cu2Cl2(CH2=CH–CH2)2O]

A new polymorph of [Cu2Cl2(CH2=CH-CH 2)2O] has been obtained by an alternating-current electrochemical synthesis starting from CuCl2 and triallylphosphite. Diallylether was obtained in statu nascendi via transetherification of triallylphosphite. The structure is monoclinic, space group P21/n, a = 7.6738(7), b = 6.5128(4), c = 18.2689(18) A, β = 91.644(11)°, V = 912.67(13) A3 (at 150 K), Z = 4; R1 = 0.0339, wR2 = 0.0822. Flexibility of the organic ligand and weak interactions copper⋯halogen have been identified as the main reasons enabling polymorphism in molecular π-complexes of copper(I). ©2008 Wiley-VCH Verlag GmbH & Co. KGaA.