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
https://doi.org/10.30970/cma5.0209
Mykhaylo LUK’YANOV, Vasyl KINZYBALO, Evgeny GORESHNIK, Oleksiy PAVLYUK, Maryan MYS’KIV
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 (Ñu2X3) nn- (X = Cl, Br), which are joined together by organic cations (H+L) (I) or surrounded by them (I²-²V). 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