By means of the alternating-current electrochemical technique 20 new copper compounds with N-allyl derivatives of ethylenediamine have been obtained and X-ray structurally investigated, among them are 10 pi-complexes of copper(I) - one compound with N-allyl- N,N,N',N'-tetramethylethylenediammonium ([H+alltmen]2+) - [(H+alltmen)Cu4Cl6], four - with N,N'-diallyl-N,N,N',N'-tetramethylethylenediammonium (dalltmen2+) - [(dalltmen)0.5Cu(NO3)2], [(dalltmen)0.5CuCl2], [(dalltmen)0.5CuCl0.72Br1.28], [(dalltmen)0.5Cu2Cl1.67Br1.33], one - with N,N,N',N'-tetraallylethylenediammonium ((H+)2tallen) - [{(H+)2tallen}0.5Cu2Cl3], one - with N,N,N,N',N'-pentaallylethylenediammonium ([H+pallen]2+) - [(H+pallen)Cu4Br6], and three - with N,N,N,N',N',N'-hexaallylethylenediammonium (hallen2+) - [(hallen)0.5CuBr2], [(hallen)0.5Cu2Br3] and [(hallen)0.5Cu2Br2.27Cl0.73]. In copper(I) pi-complexes N-allyl derivatives of ethylenediamine demonstrate a bridged behaviour: they are coordinated to the metal atoms with C=C bonds and act as mono-, di- or tetradentate ligands. Both discrete ([(dalltmen)0.5CuCl2], etc) and infinite (1D, 2D and 3D, [(hallen)0.5Cu2Br3], [(H+alltmen)Cu4Cl6] and [(dalltmen)0.5Cu2Cl1.67Br1.33], correspondingly) inorganic fragments are arised in these complexes. In the crystal structure of [(H+alltmen)Cu4Cl6] pi-coordinated [H+alltmen]2+ cations are located in cavities of two-dimensional copper(I) halide aggregate (Cu4Cl62-)n. The compounds [(dalltmen)0.5CuCl2], [(dalltmen)0.5CuCl0.72Br1.28] and [(hallen)0.5CuBr2] contain binuclear Cu2X42- anions which are connected with the ligand cations into polimeric coordination chains. In the structures of [(dalltmen)0.5Cu(NO3)2], [(H+pallen)Cu4Br6], [(hallen)0.5Cu2Br2.27Cl0.73] and [(hallen)0.5Cu2Br3] infinite inorganic chains are linked with the organic cations into two dimensional layers. Complex [(dalltmen)0.5Cu2Cl1.67Br1.33] contains a three-dimensional copper(I)halide anion (Cu2X3-)n with pi-coordinated cations of dalltmen2+ in its hollows. In the structure of [{(H+)2tallen}0.5Cu2Cl3] Cu4Cl62- the anions are connected with (H+)2tallen m4-cations into a {(H+)2tallen-Cu4Cl6-(H+)2tallen-Cu4Cl6}n network. Thus, bridged cations of N-allyl derivatives of ethylenediammonium act as linkers of the separate anionic copper(I) fragments. Crystal structures of copper(I) non-pi-complexes consist of infinite simple chains (CuX2-)n (or CuBr32- anions for [H+pallen][CuBr3]) and N-allyl derivatives of ethylenediammonium, which are connected with H-bonds. Size of organic ligand, a type of inorganic fragment, number of Cu-(C=C)-bonds and H-contacts influence markedly on a structural design of the copper(I) pi-complexes. Compared to the mainly discrete structures of copper(I) complexes with ethylenediamine itself and its some alkyl derivatives, one-dimensional ([(dalltmen)0.5CuCl2], [(hallen)0.5CuBr2], etc.), two-dimensional ([(H+alltmen)Cu4Cl6], [(dalltmen)0.5Cu(NO3)2], [(H+pallen)Cu4Br6], [(hallen)0.5Cu2Br3], etc.) and three-dimensional ([(dalltmen)0.5Cu2Cl1.67Br1.33], [{(H+)2tallen}0.5Cu2Cl3]) coordination polymers demonstrate new possibilities of Cu(I) pi-complexes crystal engineering for N-allyl derivatives of ethylenediamine. The (E)H...X bonds (X = Cl, Br, ONO2) play a significant role in a crystal structure of the complexes. For example, in [{(H+)2tallen}0.5Cu2Cl3] strong (N)H...X bonds unite structural fragments into a three-dimensional framework, and weak (C)H...X bonds fasten the bulky ligand cations. Thus, Cu-(C=C) interaction and H-bonds are two crucial factors in crystal engineering of copper(I) pi-complexes with N-allyl derivatives of ethylenediammonium, and competition between them leads to a formation of diversity of the structures discussed.
