Journal of inclusion phenomena

, Volume 2, Issue 1–2, pp 215–222 | Cite as

The structures of macrocyclic heterocyclophane inclusion complexes

  • K. Hirotsu
  • S. Kamitori
  • T. Higuchi
  • I. Tabushi
  • K. Yamamura
  • H. Nonoguchi
Original Papers

Abstract

Crystal and molecular structures of (1:1) molecular complexes of N,N′,N″,N″-tetramethyl-2, 11, 20, 29-tetraaza [3.3.3.3] paracyclophane (1) with CHCl3, CH2Cl2, CH3CN and CO2 are reported. The macrocycle has square-box structure, giving hydrophobic cavity surrounded by four benzene rings. The guest molecules are included in the cavity. The uncomplexed1 was found to have a rectangular form, indicating large conformational flexibility of1. In solution,1 is achiral because rapid R⇌S interconversion, but in solid, the macrocyclic conformation is frozen as “R”-conformer or “S”-conformer. The macrocycles with the same chirality are stacked alongb-axis to form chiral molecular columns, “R”-colums or “S”-columns. Complexes of1 crystallize differently depending on the guest molecules. “R”-columns (“S”-columns) packed alonga-axis produce “R”-layers (“S”-layers), which are further packed alongc-axis using “R”-layer to “R”-layer contact (RR) or SS and RS or SR. The crystals of1·CHCl3 are formulated as--RRR--=[R]n (Type I, chiral) and those of1·CH3CN or1·CO2 and1·CH2Cl2 are represented by [RS]n (Type IIA, racemic) and [RRSS]n (Type IIB, racemic), respectively.

Keywords

Benzene CH2Cl2 Benzene Ring Inclusion Complex CH3CN 

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References

  1. 1.(a)
    M.L. Bender and M. Komiyama,Cyclodextrin Chemistry, Springer-Verlag: West Berlin and Heidelberg, 1978.Google Scholar
  2. 1.(b)
    I. Tabushi,Acc. Chem. Res., 1982,15, 66.Google Scholar
  3. 2.(a)
    I. Tabushi, Y. Kimura, K. Yamamura,J, Am. Chem. Soc., 1981,103, 6486.Google Scholar
  4. 2.(b)
    Y. Murakami, A. Nakano, R. Miyata and Y. Matsuda,J. Chem. Soc., Perkin Trans. 1,1979, 1669.Google Scholar
  5. 3.
    I. Tabushi, Y. Kuroda and Y. Kimura,Tetrahedron Lett.,1976, 3327.Google Scholar
  6. 4.
    I. Tabushi, K. Yamamura, H. Nonoguchi, K. Hirotsu and T. Higuchi,J. Am. Chem. Soc., 1984,106, 2621.Google Scholar
  7. 5.
    S.J. Abott, A.G.M. Barret, C.R.A. Godfrey, S.B. Kalindjian, G.W. Simpson and D.J. Williams,J. Chem. Soc., Chem. Commun.,1982, 796.Google Scholar
  8. 6.
    Crystals of uncomplexed1 are monoclinic, space group P21/a witha=21.491 (2),b=15.123 (1),c=10.020 (1) Å and β=97.26(1)o; Z=4. The structure was solved by direct method and refined to R=0.083 for 1269 reflections with I>3σ(I). Full details will be published elsewhere.Google Scholar
  9. 7.
    The following library of major crystallographic programs was employed: MULTAN, G. Germain, P. Main and M.M. Woolfson,Acta Crystallogr., 1970, B26, 274; ORFLS, W.R. Busing, K.O. Martin and H.A. Levy, Oak Ridge National Laboratory Report ORNL-TM-305; ORTEP, C.K. Johnson, Oak Ridge National Laboratory Report ORNL-TM-3794.Google Scholar
  10. 8.
    W.C. Hamilton,Acta Crystallogr., 1959,12, 609.Google Scholar
  11. 9.
    N.L. Allinger,J. Am. Chem. Soc., 1977,99, 8127. MM2 is available from Indiana University's Quantum Chemistry Program Exchange as program number 395.Google Scholar

Copyright information

© D. Reidel Publishing Company 1984

Authors and Affiliations

  • K. Hirotsu
    • 1
  • S. Kamitori
    • 1
  • T. Higuchi
    • 1
  • I. Tabushi
    • 2
  • K. Yamamura
    • 2
  • H. Nonoguchi
    • 2
  1. 1.Department of ChemistryOsaka City UniversityOsakaJapan
  2. 2.Department of Synthetic ChemistryKyoto UniversityKyotoJapan

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