π-Complexes of copper(I) halides with 3-(allylamino)-(C3H5NHC2H4CN, Apn) and 3-(diallylamino)-((C3H5)2NC2H4CN, Dapn)-propanenitrile. syntheses and crystal structures of compounds [CuCl(Apn)], [(H+Apn)Cu2Cl3], [(H+Dapn)CuCl2], and [(H+Dapn)CuBr2

Abstract

The π-complexes [CuCl(C3H5NHC2H4CN)] (I), [(C3H5NH2C2H4CN)Cu2Cl3] (II), [((C3H5)2NHC2H4CN)CuCl2] (III), and [((C3H5)2NHC2H4CN)CuBr2] (IV) are obtained as single crystals by the ac electrochemical synthesis on copper wire electrodes from ethanolic solutions of 3-(allylamino)propanenitrile, 3-(diallylamino)propanenitrile, and CuX2 (X = Cl, Br). Their crystal structures are determined. The crystals of compounds I, III, and IV are monoclinic, space group P21/c, Z = 4. The crystals of compound II are triclinic, space group P\(\bar 1\), Z = 2. The unit cell parameters are a = 11.125(4), b = 8.769(4), c = 8.570(4) A, β = 90.94(4)°, V = 835.9(6) A3 (I); a = 6.2566(4), b = 7.5975(6), c = 11.1251(8) A, α = 90.896(6)°, β = 92.827(5)°, γ = 94.340(5)°, V = 526.57(7) A3 (II); a = 11.656(4), b = 6.992(4), c = 14.681(5) A, β = 100.89(4)°, V = 1174.9(9) A3 (III); a =11.845(4), b = 7.282(4), c=14.855(5) A, β = 100.37(4)°, V = 1260.4(9) A3 (IV). The coordination mode of the Cu(I) atom in complex I includes two halogen atoms, the C=C bond, and the secondary amine N atom. The coordination environment in isostructural crystals of complexes III and IV is formed by the C=C bond and three halogen atoms as in complex II.