Skip to main content
SpringerLink
Log in

Architecture of framework copper(I) halide π-complexes with N-allyl-N,N,N′,N′-tetramethyl-ethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium: Synthesis and crystal structure of [{C2H4N2(H+)×(CH3)4(C3H5)} Cu4Cl6] and [{C2H4N2(CH3)4(C3H5)2}0.5Cu2Cl1.67Br1.33]

  • Published:
Journal of Structural Chemistry Aims and scope Submit manuscript

Abstract

N,N,N′,N′-tetramethylethylenediamine is obtained by the reaction of ethylenediamine with formaldehyde and formic acid (the Eschweiler-Clarke reaction) and then alkylated with allyl chloride (or bromide) in a ratio of 1:1 or 1:2 to obtain N-allyl-N,N,N′,N′-tetramethylethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium bromide respectively. [{C2H4N2(H+)(CH3)4(C3H5)}Cu4Cl6] (1) and [{C2H4N2(CH3)4(C3H5)2}0.5Cu2Cl1.67Br1.33] (2) π-complexes are obtained from alcohol solutions containing an ethylenediamine derivative and copper(II) chloride by ac-electrochemical synthesis on copper wire electrodes. An XRD study of the complexes is carried out. The crystals are monoclinic; 1: P21/n space group, a = 9.0081(6) Å, b = 12.5608(7) Å, c = 16.8610(10) Å, β = 102.061(3)°, V = 1865.7(2) Å3, Z = 4; 2: C2/c space group, a = 14.462(2) Å, b = 12.519(1) Å, c = 12.762(2) Å, β = 107.861(5)°, V = 2199.1(4) Å3, Z = 8. The structure of 1 consists of infinite copper halide networks with four crystallographically independent copper atoms, one of which coordinates the double bond of the allyl group of the ligand. The [C2H4N2(H)(CH3)4(C3H5)]2+ cations are attached above and below the plane of the network. The individual fragments are bonded via an extensive system of (N)H…Cl and (C)H…Cl hydrogen bonds. The structure of 2 contains a three-dimensional copper halide framework whose cavities contain the [C2H4N2(CH3)4(C3H5)2]2+ cations that are π-coordinated with copper(I) atoms. In both structures, the Cu(I) atom that coordinates the C=C bond has a trigonal-pyramidal coordination environment consisting of the double C=C bond of the corresponding ligand and three halogen atoms. The other Cu(I) atoms have a tetrahedral environment consisting solely of halogen atoms. The Cu-(C=C) distance is 1.958(1) Å, (1) and 1.974(1) Å (2).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. I. Bertini, P. Dapporto, D. Gatteschi, et al., J. Chem. Soc., Dalton Trans., No. 9, 1409 (1979).

  2. J. R. Anacona, C. Gutierrez, and C. Rodriguez-Barbarin, Monatsh. Chem., 135, No. 7, 785 (2004).

    CAS  Google Scholar 

  3. R. D. Ball, D. Hall, C. E. F. Rickard, et al., J. Chem. Soc. A, 1435 (1967).

  4. M. Pasquali, C. Floriani, and A. Gaetani-Manfredotti, Inorg. Chem., 19, No. 5, 1191 (1980).

    Article  CAS  Google Scholar 

  5. A. Johansson, M. Hakansson, and S. Jagner, Chem. Eur. J., 11, No. 18, 5311 (2005).

    Article  CAS  Google Scholar 

  6. E. D. Estes, W. E. Estes, W. E. Hatfield, et al., Inorg. Chem., 14, No. 1, 106 (1975).

    Article  CAS  Google Scholar 

  7. M. R. Churchill, G. Davies, M. A. El-Sayed, et al., Inorg. Chem., 23, No. 6, 783 (1984).

    Article  CAS  Google Scholar 

  8. M. M. Monchak, A. V. Pavlyuk, V. V. Kinzhibalo, et al., Koordinatts. Khim., 35, No. 6, 414 (2009).

    Google Scholar 

  9. M. Monchak, E. Goreshnik, and M. Mys’kiv, Visn. Lviv. Univ. Ser. Khim., No. 50, 36 (2009).

  10. M. Monchak, A. V. Pavlyuk, V. V. Kinzhibalo, et al., Koordinats. Khim., 36, No. 3, 200 (2010).

    Google Scholar 

  11. K. Weygand and G. Hilgetag, Organisch-Chemische Experimentierkunst, Barth, Leipzig (1964).

    Google Scholar 

  12. B. M. Mykhalichko and M. G. Mys’kiv, Patent of Ukraine No. UA 25450A, Bull., No. 6 (1998).

  13. CrystalClear: Rigaku Corporation, The Woodlands, Texas, USA (1999).

  14. R. C. Clark and J. S. Reid, Acta Cryst., A51, No. 6, 887 (1995).

    CAS  Google Scholar 

  15. A. Altomare, G. Cascarano, C. Giacovazzo, et al., J. Appl. Cryst., 27, 435 (1994).

    Google Scholar 

  16. G. M. Sheldrick, SHELXS-97 and SHELXL-97, Program for the Solution and Refinement of Crystal Structures, Univ. Göttingen, Germany (1997).

    Google Scholar 

  17. G. R. Desiraju and T. Steiner, Weak Hydrogen Bond in Structural Chemistry and Biology, Oxford University Press, Oxford (1999).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Ivan Franko National University of Lviv, Lviv, Ukraine

    M. M. Monchak & M. G. Mys’kiv

  2. JoŽef Stefan Institute, Ljubljana, Slovenia

    E. A. Goreshnik

Authors
  1. M. M. Monchak
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. A. Goreshnik
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. G. Mys’kiv
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. G. Mys’kiv.

Additional information

Original Russian Text Copyright © 2012 by M. M. Monchak, E. A. Goreshnik, and M. G. Mys’kiv

__________

Translated from Zhurnal Strukturnoi Khimii, Vol. 53, No. 1, pp. 124–129, January–February, 2012.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Monchak, M.M., Goreshnik, E.A. & Mys’kiv, M.G. Architecture of framework copper(I) halide π-complexes with N-allyl-N,N,N′,N′-tetramethyl-ethylenediaminium and N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium: Synthesis and crystal structure of [{C2H4N2(H+)×(CH3)4(C3H5)} Cu4Cl6] and [{C2H4N2(CH3)4(C3H5)2}0.5Cu2Cl1.67Br1.33]. J Struct Chem 53, 119–124 (2012). https://doi.org/10.1134/S0022476612010155

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0022476612010155

Keywords

Search

Navigation