Crystal structure of β-cyclodextrin-4-chlorobenzoic acid complex: unusual C–Cl⋯π interaction between 4-chlorobenzoic acids in β-cyclodextrin dimer

doi:10.1016/j.cclet.2011.01.016

Chinese Chemical Letters

Volume 22, Issue 7, July 2011, Pages 847-850

https://doi.org/10.1016/j.cclet.2011.01.016 Get rights and content

Abstract

The inclusion complex of β-cyclodextrin (β-CD) with 4-chlorobenzoic acid was synthesized and its crystal structure was determined by single crystal X-ray diffraction under cryogenic condition. The complex contains two β-CDs, two 4-chlorobenzoic acids and twenty-nine water molecules in the asymmetric unit, and can be formulated as 2(C₄₂H₇₀O₃₅)·2(C₇H₅O₂Cl)·29(H₂O). In the crystal lattice, two β-CDs form a face-to-face dimer jointed together through hydrogen bonding between the secondary hydroxyl groups of β-CDs. Two 4-chlorobenzoic acid molecules which contact by C–Cl⋯π interactions are included in the β-CD dimer cavity. The β-CD dimers are arranged in brickwork-like pattern along the crystallographic a-axis. The effect of guest molecule length on the inclusion geometry was discussed by comparative study of some β-CD complexes containing similar guests.

Section snippets

Experimental

The mixture of β-CD (0.5 mmol) and 4-chlorobenzoic acid (0.5 mmol) in 40 mL distilled water was stirred continuously for 6 h at 55 °C, which afforded a solution of the title inclusion complex. Plate-like crystals suitable for X-ray diffraction experiments were obtained by slow evaporation of the complex solution at 40 °C. A crystal was encased in vaseline for avoiding dehydration and then was flash frozen at 150 K for measuring. Diffraction data collection was performed on an Oxford Diffraction

Results and discussion

The asymmetric unit consists of two β-CDs, two 4-chlorobenzoic acids and twenty-nine water molecules. The two β-CD molecules constitute a dimer by face-to-face contact of their secondary sides [9], in which two 4-chlorobenzoic acid molecules are included (Fig. 1). Twenty-nine water molecules are distributed in the interstices between the dimers. The β-CD dimers are linked together via hydrogen bonding to form layers in the crystallographic bc-plane. The layers are further stacked along the

Acknowledgments

We are grateful for the financial support from the Natural Science Foundation of Hainan Province (no. 808145) and Doctoral Foundation of Hainan Normal University (no. 103303).

References (15)

P.B. Fai et al.
Environ. Pollut.
(2009)
Z.X. Yang et al.
Carbohydr. Res.
(2008)
K. Harata
Chem. Rev.
(1998)
Y. Liu et al.
J. Org. Chem.
(2004)
Y. Liu et al.
Org. Biomol. Chem.
(2005)
S. Makedonopoulou et al.
Acta Crystallogr. B
(2000)
D. Mentzafos et al.
Acta Crystallogr. B
(1991)
R. Breslow et al.
Chem. Rev.
(1998)
K. Uekama et al.
Chem. Rev.
(1998)
Y. Chen et al.
Chem. Soc. Rev.
(2010)

There are more references available in the full text version of this article.

Cited by (10)

Adsorption of polyhaloalkane vapors by adaptive macrocycle crystals of WreathArene through C-halogen⋯π interactions
2022, Chinese Chemical Letters
Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals, therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable. Here we report a novel macrocycle WreathArene, a fluorinated C₃-symmetrical [1₆]-paracyclophane. In the crysalline state, WreathArene features guest-adaptive polymorphism for polyhaloalkanes including chloroform, tribromomethane, 1,1,2-trichloroethane, and 1,2-dibromoethane. Non-covalent C-halogen⋯π interactions are observed in all of these host-guest structures. Based on these properties, the activated WreathArene crystals can be utilized as a selective and recyclable adsorbent for polyhaloalkane vapors with excellent capacity under user-friendly conditions.
The structural analysis of the inclusion complex of β-cyclodextrin with m-nitrophenoxyacetic acid
2013, Chinese Chemical Letters
Citation Excerpt :
Therefore, a great deal of effort has been concentrated on the structure and interactions between the guest molecules and CD. Several weak intermolecular interactions between host and guest, such as hydrogen-bonding interactions, van der Waals interactions, hydrophobic, electrostatic, and dipole–dipole, can cooperatively contribute to the molecular inclusion process [16–22]. At the same time, the inclusion behavior is also influenced by the shape and size of the guest.
The inclusion complex of β-cyclodextrin with m-nitrophenoxyacetic acid was studied by single crystal X-ray diffraction, 2D NMR spectroscopy and semi-empirical methods AM1. The crystallographic study shows that two β-cyclodextrins are held together by hydrogen bonds to form head-to-head dimers. The disordered guest molecule adjusts itself to attain the most stable accommodation into the cavity in which the nitro group is located at the dimer interface while the carboxyl group is buried in the primary hydroxyl groups of β-cyclodextrin. The guest inside the cavity is disordered over two sites and exhibits mobility. Moreover, 2D NMR spectroscopy and theoretical study show the same inclusion behavior. In comparison to the inclusion complex of β-cyclodextrin with p-nitrophenoxyacetic acid, the host-guest stoichiometries are different, i.e., 2:1 for m-nitrophenoxyacetic acid and 1:1 for p-nitrophenoxyacetic acid, while the inclusion orientation and the packing pattern of the host are similar in both complexes.
Synthesis and properties of template-promoted switchable dithienylethene-based macrocycles
2013, Chinese Chemical Letters
Citation Excerpt :
In recent decades, macrocyclic chemistry has been developed into a major field of supramolecular chemistry due to its important role playing in host-guest chemistry [1–4], supramolecular self-assembly [5,6] and so on [7].
Three switchable macrocycles based on photochromic dithienylethene were synthesized under the template of dibenzylammonium hexafluorophosphate. Their structure were well-confirmed by NMR, ESI-MS and X-ray diffraction. Their photochromism indicated that they showed good reversibility in solution. Additionally, the theoretical calculation suggested that photoirradiation can change the cavity of macrocycles.
Rac-11-t-Butoxy-1,4-dihydro-1,4-methanoanthracene: A two-dimensional framework structure built from CH⋯O and CH⋯π hydrogen bonds
2012, Chinese Chemical Letters
The title compound rac-11-t-butoxy-1,4-dihydro-1,4-methanoanthracene (C₁₉H₂₀O, M_r = 264.35) has been synthesized and characterized by FT-IR, ¹H NMR, HRMS spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2₁/n, with a = 13.5240(10), b = 8.3453(6), c = 13.9604(9) Å, β = 100.0190(10)°. The structure of the title compound comprises a norbornene unit with a t-butoxy group, having a naphthalene ring fused on one side. The naphthalene is essentially planar with a maximum deviation of 0.032(2) Å for atom C(3). In the crystal, inversion-related molecules are linked by pairs of CH⋯O hydrogen bonds, forming a cyclic dimer with $R_{2}^{2}$ (16) graph-set motif. The CH⋯π interactions are also observed, linking the molecules into a continuous two-dimensional framework structure.
7-Methoxyindan-1-one
2012, Acta Crystallographica Section E: Structure Reports Online
3-Oxo-2,3-dihydro-1H-inden-4-yl acetate
2012, Acta Crystallographica Section E: Structure Reports Online

View all citing articles on Scopus

View full text

Crystal structure of β-cyclodextrin-4-chlorobenzoic acid complex: unusual C–Cl⋯π interaction between 4-chlorobenzoic acids in β-cyclodextrin dimer

Abstract

Section snippets

Experimental

Results and discussion

Acknowledgments

Environ. Pollut.

Carbohydr. Res.

Chem. Rev.

J. Org. Chem.

Org. Biomol. Chem.

Acta Crystallogr. B

Acta Crystallogr. B

Chem. Rev.

Chem. Rev.

Chem. Soc. Rev.