Copper(I) halide complexes with ethylenediaminium L0(H+)2, N,N,N′,N′-tetraallylethylenediaminium L4(H+)2, and N,N,N,N′,N′-pentaallylethylenediaminium L5(H+). Synthesis and crystal structures of the complexes [L0(H+)2]0.5CuCl2, [L0(H+)2]0.5CuBr1.67Cl0.33, [{L4(H+)2}0.5Cu2Cl3], and [L5(H+)Cu4Br6]

Alkylation of ethylenediamine with allyl bromide in the presence of NaHCO3 in benzene-ethanol and acetone-ethanol gave N,N,N′,N′-tetraallylethylenediamine L4 and N,N,N,N′,N′-pentaallylethylenediaminium bromide (L5(H+)Br2), respectively. The ac electrochemical synthesis at copper wire electrodes in solutions of copper(II) halide and an appropriate ligand yielded single crystals of Cu(I) complexes with ethylenediaminium ([L0(H+)2]0.5CuCl2 (I) and [L0(H+)2]0.5CuBr1.67Cl0.33 (II)) and its N-allyl derivatives N,N,N′,N′-tetraallylethylenediaminium ([{L4(H+)2}0.5Cu2Cl3] (III)) and N,N,N,N′,N′-pentaallylethylenediaminium ([L5(H+)Cu4Br6] (IV)). The crystal structures of complexes I–IV were determined by X-ray diffraction. The isostructural crystals of complexes I and II are triclinic, space group P\( \bar 1 \), Z = 2. For I: a = 5.936(3), b = 6.387(3), c = 7.126(4) A, α = 67.82(4)°, β = 72.98(4)°, γ = 67.55(4)°, V = 227.7(2) A3. For IIa = 6.110(3), b = 6.657(3), c = 7.309(3) A, α = 68.40(3)°, β = 72.38(3)°, γ = 67.23(3)°, V = 250.4(2) A3. In structures I and II, the organic cations are between infinite anionic chains (Cu2−)n. The crystals of π-complex III are triclinic, space group P\( \bar 1 \), a = 6.851(4), b = 8.729(4), c = 9.960(4) A, α = 98.25(3)°, β = 102.29(3)°, γ = 107.30(3)°, V = 541.8(5) A3, Z = 2. In structure III, all the four allyl groups are π-coordinated by the metal atoms of four discrete anions Cu4Cl62−. The crystals of π-complex IV are monoclinic, space group C2/c, a = 15.228(5), b = 17.095(6), c = 20.182(6) A, β = 92.43(4)°, V = 5249(3) A3, Z = 8. Only two of five allyl groups at the same N atom are coordinated by copper(I) atoms. Structure IV contains a complex inorganic fragment of the formula (Cu4Br62−)n.