Copper(I) complexes with 3-(allylamino)-, 3-(diallylamino)-,
3-[(2-hydroxyethyl)(allyl)amino]- and 3-[(2-hydroxyethyl)amino]- propanenitriles. Synthesis and crystal structure of [{C3H5NH(H+)C2H4CN}Cu2Br3], [{(C3H5)2N(H+)C2H4CN}CuCl1.94Br0.06], [{HOC2H4NH(H+)C2H4CN}CuCl2] and [{HOC2H4(C3H5)N(H+)C2H4CN}CuCl2]

 

Chem. Met. Alloys 5 (2012) 66-76

 

Mykhaylo LUKYANOV, Vasyl KINZYBALO, Evgeny GORESHNIK, Oleksiy PAVLYUK, Maryan MYSKIV

 

Four crystalline copper(I) complexes with N-derivatives of propanenitrile: [{C3H5NH(H+)C2H4CN}Cu2Br3] (I), [{(C3H5)2N(H+)C2H4CN}CuCl1.94Br0.06] (II), [{HOC2H4NH(H+)C2H4CN}CuCl2] (III) and [{HOC2H4(C3H5)N(H+)C2H4CN}CuCl2] (IV), have been obtained (by the alternating current electrochemical technique from alcohol solutions of the organic ligand and CuCl2∙2H2O or CuBr2) and investigated by X-ray diffraction. Crystals of compound I are triclinic, space group P-1, Z = 2, a = 6.5520(7), b = 7.8642(8), c = 11.2370(12) Å, α = 90.694(6), β = 94.427(6), γ = 93.690(6), V = 575.99(10) Å3. Crystals of compounds II-IV are monoclinic. For II and IV the space group is P21/c, Z = 4. For II: a = 11.6518(4), b = 7.0086(2), c = 14.6765(5) Å, β = 100.965(13), V = 1176.64(7) Å3; IV: a = 11.001(3), b = 7.017(2), c = 14.653(4) Å, β = 97.19(3), V = 1122.2(5) Å3. For III the space group is P2/c, Z = 4, a = 7.452(2), b = 7.642(2), c = 15.867(5) Å, β = 95.43(3), V = 899.5(4) Å3. The structures of the coordination compounds I-IV possess distinct polymer anionic chains (CuX2)nn- or (u2X3) nn- (X = Cl, Br), which are joined together by organic cations (H+L) (I) or surrounded by them (I-V). Hydrogen bonding play a significant role in the stabilization of the structures.

 

 

Projection of the structure of [{C3H5NH(H+)C2H4CN}Cu2Br3]

Symmetry codes: (i) −1+x, y, z, (ii) −1+x, y, −1+z

 

Keywords

Copper(I) / π- and σ-Complexes / β-Aminonitriles / Crystal structure / Electrochemical technique