[Journal logo]

Volume 69 
Part 7 
Pages o1001-o1002  
July 2013  

Received 15 May 2013
Accepted 24 May 2013
Online 8 June 2013

Key indicators
Single-crystal X-ray study
T = 123 K
Mean [sigma](C-C) = 0.005 Å
Disorder in main residue
R = 0.078
wR = 0.249
Data-to-parameter ratio = 24.0
Details
Open access

Calixarene-based molecular capsule from olefin metathesis

aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
Correspondence e-mail: rbutcher99@yahoo.com

The reaction of tetrakis(allyloxy)calix[4]arene with the first-generation Grubbs catalyst, followed by catalytic hydrogenation, gave the novel bis-calixarene 15,20,46,51,64,69,74,79-octaoxatridecacyclo[32.28.8.83,28.113,53.122,44.09,14.021,26.038,70.040,45.052,57.059,63.07,80.032,73]octaconta-1(63),3,5,7(80),9(14),10,12,21,23,25,28(73),29,31,34,36,38(70),40,42,44,52,54,56,59,61-tetracosaene benzene monosolvate, C72H72O8·C6H6. The structure consists of two calix[4]arene units connected by four-carbon chains at each of the four O atoms on their narrow rims, to form a cage. Each of the calix[4]arene units has a flattened cone conformation in which two of the opposite aryl groups are closer together and nearly parallel [dihedral angle between planes = 7.35 (16)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 72.20 (8)°]. While the cavity contains no solvent or other guest molecule, there is benzene solvent molecule in the lattice. Two of the alkyl linking arms were disordered over two conformations with occupancies of 0.582 (3)/0.418 (3) and 0.33 (4)/0.467 (4). They were constrained to have similar metrical and thermal parameters.

Related literature

For literature related to the use of calixarenes as easily isolable reaction products, see: Asfari et al. (2001[Asfari, Z., Böhmer, V., Harrowfield, J. & Vicens, J. (2001). In Calixarenes 2001. Dordrecht: Kluwer Academic Publishers.]); Gutsche (2008[Gutsche, C. D. (2008). Calixarenes: An Introduction, 2nd ed., Monographs in Supramolecular Chemistry, edited by J. F. Stoddard. Cambridge: The Royal Society of Chemistry.]). For literature related to the preparation of bridged calixarenes, see: Yang & Swager (2007[Yang, Y. & Swager, T. M. (2007). Macromolecules, 40, 7437-7440.]); Hailu et al. (2012[Hailu, S. T., Butcher, R. J., Hudrlik, P. F. & Hudrlik, A. M. (2012). Acta Cryst. E68, o1833-o1834.]). For literature related to the conformation of calixarenes, see: Arduini et al. (1995[Arduini, A., Fanni, S., Manfredi, G., Pochini, A., Ungaro, R., Sicuri, A. R. & Ugozzoli, F. (1995). J. Org. Chem. 60, 1448-1453.], 1996[Arduini, A., McGregor, W. M., Pochini, A., Secchi, A., Ugozzoli, F. & Ungaro, R. (1996). J. Org. Chem. 61, 6881-6887.]); Drew et al. (1997[Drew, M. G. B., Beer, P. D. & Ogden, M. I. (1997). Acta Cryst. C53, 472-474.]). For literature related to starting material and catalyst used, see: Ho et al. (1996[Ho, Z., Ku, M., Shu, C. & Lin, L. (1996). Tetrahedron, 52, 13189-13200.]); Vougioukalakis & Grubbs (2010[Vougioukalakis, G. C. & Grubbs, R. H. (2010). Chem. Rev. 110, 1746-1787.]).

[Scheme 1]

Experimental

Crystal data
  • C72H72O8·C6H6

  • Mr = 1143.40

  • Monoclinic, P 21 /c

  • a = 14.8804 (10) Å

  • b = 17.3004 (11) Å

  • c = 12.1888 (8) Å

  • [beta] = 103.929 (7)°

  • V = 3045.6 (3) Å3

  • Z = 2

  • Cu K[alpha] radiation

  • [mu] = 0.62 mm-1

  • T = 123 K

  • 0.87 × 0.35 × 0.03 mm

Data collection
  • Agilent Xcalibur (Ruby, Gemini) diffractometer

  • Absorption correction: analytical (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, Oxfordshire, England.]; Clark & Reid, 1995[Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.]) Tmin = 0.795, Tmax = 0.982

  • 9972 measured reflections

  • 9972 independent reflections

  • 5548 reflections with I > 2[sigma](I)

  • Rint = 0.000

Refinement
  • R[F2 > 2[sigma](F2)] = 0.078

  • wR(F2) = 0.249

  • S = 1.00

  • 9972 reflections

  • 415 parameters

  • 10 restraints

  • H-atom parameters constrained

  • [Delta][rho]max = 1.03 e Å-3

  • [Delta][rho]min = -0.24 e Å-3

Data collection: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012[Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, Oxfordshire, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG5315 ).


Acknowledgements

RJB wishes to acknowledge the NSF-MRI program (grant CHE-0619278) for funds to purchase the diffractometer. STH wishes to acknowledge the Howard University Graduate School for a Teaching Assistantship.

References

Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, Oxfordshire, England.
Arduini, A., Fanni, S., Manfredi, G., Pochini, A., Ungaro, R., Sicuri, A. R. & Ugozzoli, F. (1995). J. Org. Chem. 60, 1448-1453.  [CrossRef] [ChemPort]
Arduini, A., McGregor, W. M., Pochini, A., Secchi, A., Ugozzoli, F. & Ungaro, R. (1996). J. Org. Chem. 61, 6881-6887.  [CrossRef] [PubMed] [ChemPort]
Asfari, Z., Böhmer, V., Harrowfield, J. & Vicens, J. (2001). In Calixarenes 2001. Dordrecht: Kluwer Academic Publishers.
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897.  [CrossRef] [IUCr Journals]
Drew, M. G. B., Beer, P. D. & Ogden, M. I. (1997). Acta Cryst. C53, 472-474.  [CSD] [CrossRef] [IUCr Journals]
Gutsche, C. D. (2008). Calixarenes: An Introduction, 2nd ed., Monographs in Supramolecular Chemistry, edited by J. F. Stoddard. Cambridge: The Royal Society of Chemistry.
Hailu, S. T., Butcher, R. J., Hudrlik, P. F. & Hudrlik, A. M. (2012). Acta Cryst. E68, o1833-o1834.  [CSD] [CrossRef] [ChemPort] [IUCr Journals]
Ho, Z., Ku, M., Shu, C. & Lin, L. (1996). Tetrahedron, 52, 13189-13200.  [CrossRef] [ChemPort] [Web of Science]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Vougioukalakis, G. C. & Grubbs, R. H. (2010). Chem. Rev. 110, 1746-1787.  [Web of Science] [CrossRef] [ChemPort] [PubMed]
Yang, Y. & Swager, T. M. (2007). Macromolecules, 40, 7437-7440.  [Web of Science] [CSD] [CrossRef] [ChemPort]


Acta Cryst (2013). E69, o1001-o1002   [ doi:10.1107/S1600536813014438 ]

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.