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1:2 and 2:1 Stoichiometric Inclusion Complexes of 1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol and p-Anisaldehyde

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Abstract

1:2 and 2:1 stoichiometric complexes of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (DD) and p-anisaldehyde were presented in this paper. 2:1 inclusion complex of DD with p-anisaldehyde (denote 1) was fortuitously obtained from the volatile oil of medicine herb Zanthoxylum schinifolium Sieb.et Zucc. 1:2 inclusion complex of DD with p-anisaldehyde (denote 2) was obtained under ordinary crystallization conditions. The results of single crystal X-ray diffraction show that complex 1 is triclinic, space group Pī, whereas the complex 2 is monoclinic, space group P21/n. In the complex of 1, 1D zigzag ribbon host framework is constructed through a closed hydrogen bonding network formed by DD molecules themselves and p-anisaldehyde molecules are accommodated into the tunnel enclosed by 1D zigzag ribbons. In the complex of 2, DD and p-anisaldehyde are connected with each other via hydrogen bonding, forming a layer-type structure. DD molecule exhibits gauche conformation in complex 1 and antiperiplanar conformation in complex 2, which are regarded as supramolecular conformation stereoisomers.

Graphical Abstract

1:2 and 2:1 stoichiometric complexes (1 and 2) of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (DD) and p-anisaldehyde were presented in this study. DD molecule exhibits gauche conformation in complex 1 and antiperiplanar conformation in complex 2, which are regarded as supramolecular conformation stereoisomers.

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Scheme 1
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Notes

  1. The complex 1 of DD complex was concomitant side-product in the process of including the component of 4-allylanisole from the medicine herb Zanthoxylum schinifolium Sieb.et Zucc: 0.5 g DD, 2.0 g volatile oil of Zanthoxylum schinifolium Sieb.et Zucc and 2.5 mL diethyl ether were placed in a 10 mL Erlenmeyer flask which was shaken until the contents were dissolved; then 3.0 mL petroleum ether were added and the flask was allowed to stand for a week. The crystals with different crystal shapes were separated under the microscope, in which a very small amount of block-shaped and pale-yellow crystals are complex 1, m.p. ca. 84–85 °C. (d) Cell parameters of DD complex with 4-allylanisole: a = 13.011(14) Å, b = 14.807(4) Å, c = 16.873(6) Å, α = 100.82(2)º, β = 105.06(2)º, γ = 111.905(18)º, V = 2760.3(15) Å3, Dc = 1.175 Mg·m−3.

  2. Gas chromatogram was used to detect the separation effect of the active component from the inclusion complex, there are two peaks (the retain time for two peaks are 12.29 min and 18.14 min) corresponding to two different isolated components in the GC chromatogram, thus, the isolated components are mixture of 94.5% 4-allylanisole and 5.4% p-anisaldehyde.

  3. The crystal structures were determined from single-crystal X-ray diffraction data, including a redetermination of the structure of the complex 2 of DD complex with p-anisaldehyde. Data collection was carried out on a Bruker Smart diffractometer (CCD detector; MoKα radiation; graphite monochromated) using φ-ω scan at ambient temperatures. Saint program and SADABS program were used to carry out the data integration and the empirical absorption corrections. The crystal structures were solved by direct methods and refined by full-matrix least-squares methods by using SHELXS-97 program. During the refinement of complex 1, the guest p-anisaldehyde molecules always occupy two positions. Attempts to refine with lower occupancy for the atoms of each p-anisaldehyde led to significantly decrease R factor. The occupancies for the two p-anisaldehyde molecules in the two positions are assigned 0.45 and 0.55, respectively. Hydrogen atoms were located in difference Fourier maps and were included in the final structure refinement calculations. All non-H atoms were refined anisotropically. Table 1 gives crystal data and details of collection and refinement for both DD complexes. Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC No. 714721 and 714722 for complex 1 and 2, respectively. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:-44-1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).

  4. The high-quality powder X-ray diffraction data were recorded at ambient temperature in transmission mode on a Bruker D8 diffractometer [CuKα1, Ge-monochromated; linear position-sensitive detector covering 12º in 2θ; 2θ range, 5º–40º; step size, 0.017º; data collection time, 6 h; foil sample holder].

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Acknowledgments

This study was supported by the National Science Foundation of China, No. 20373031.

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  1. College of Chemistry, Liaoning University, Shenyang, 110036, People’s Republic of China

    Fang Guo & Wen-Sheng Guo

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  1. Fang Guo
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  2. Wen-Sheng Guo
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Correspondence to Fang Guo.

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Guo, F., Guo, WS. 1:2 and 2:1 Stoichiometric Inclusion Complexes of 1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol and p-Anisaldehyde. J Chem Crystallogr 41, 1774–1779 (2011). https://doi.org/10.1007/s10870-011-0172-x

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