Copper(I) complexes with 3,3′-iminodipropanenitrile and 3-(diallylamino)propanenitrile: synthesis and crystal structure of σ-[{(NH(H+)(C2H4CN)2}Cu3Cl4] and π-,σ-[Cu((C3H5)2NC2H4CN)ClO4] compounds

 

Chem. Met. Alloys 5 (2012) 173-180

https://doi.org/10.30970/cma5.0227

 

Mykhaylo LUK’YANOV, Evgeny GORESHNIK, Oleksiy PAVLYUK, Maryan MYS’KIV

 

Starting from ethanolic or water-propanolic solutions of 3,3′-iminodipropionitrile (L1), 3-(diallylamino)propanenitrile (L2), and CuCl2·2H2O or Cu(ClO4)2·6H2O, respectively, two complexes, [(NH(H+)(C2H4CN)2Cu3Cl4] (I) and [Cu((C3H5)2NC2H4CN)ClO4] (II), were obtained by the alternating current electrochemical technique and investigated by single crystal X-ray diffraction. The crystal structures of I and II are monoclinic, for I: space group P21/n, a = 8.9700(2), b = 14.3951(4), c = 10.0156(3) Å, β = 94.056(1)°, V = 1290.02(6) Å3, Z = 4; for II: space group Cm, a = 10.0916(8), b = 8.1061(7), c = 8.4207(7) Å, β = 116.581(5)°, V = 616.03(5) Å3, Z = 2. The coordination of the Cu(I) atoms in complex I includes three Cl atoms and the N atom of a cyanogroup. Cations H+L1 connect separate corrugated layers (Cu3Cl4)n into a framework.

The coordination environment of the copper(I) atom in complex II is formed by two C=C bonds of the allyl groups of one molecule L2, the nitrile N atom of another molecule L2, and the apical O atom of a ClO4 anion. The inorganic anions ClO4 also interconnect the metalorganic ribbons via O...H-C hydrogen bonds.

 

 

Projection of the structure of [Cu((C3H5)2NC2H4CN)ClO4]

Symmetry codes: (i) x, −y, z; (ii) −1+x, y, −1+z;(iii) 1/2+x, −1/2+y, −1+z; (iv) x, 1y, z.

 

Keywords

Copper(I) / π- and σ-Complexes / Crystal structure / 3-Aminopropanenitriles / àñ-Electrochemical technique