New fluorous ponytailed 4-[(2,2,2-trifluoroethoxy)methyl]pyridinium halide salts

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• 作者：Norman Lu ; Mani Alagesan ; Chi-Liang Ho ; Rong-Jyun Wei ; Chih-Chieh Kung ; Jung-Shan Chang ; Yuh-Sheng Wen and Ling-Kang Liu
• 关键词：IR spectroscopy ; synthon ; hydrogen halides ; crystal structure ; fluorous ponytailed pyridine ; blue shift ; bifurcated hydrogen bonding
• 刊名：Acta Crystallographica Section C
• 出版年：2016
• 出版时间：December 2016
• 年：2016
• 卷：72
• 期：12
• 页码：1007-1011
• 全文大小：773K
• ISSN：1600-5759

文摘

It is possible that fluorous compounds could be utilized as directing forces in crystal engineering for applications in materials chemistry or catalysis. Although numerous fluorous compounds have been used for various applications, their structures in the solid state remains a lively matter for debate. The reaction of 4-[(2,2,2-trifluoroethoxy)methyl]pyridine with HX (X = I or Cl) yielded new fluorous ponytailed pyridinium halide salts, namely 4-[(2,2,2-trifluoroethoxy)methyl]pyridinium iodide, C₈H₉F₃NO⁺·I⁻, (1), and 4-[(2,2,2-trifluoroethoxy)methyl]pyridinium chloride, C₈H₉F₃NO⁺·Cl⁻, (2), which were characterized by IR spectroscopy, multinuclei (¹H, ¹³C and ¹⁹F) NMR spectroscopy and single-crystal X-ray diffraction. Structure analysis showed that there are two types of hydrogen bonds, namely N—H…X and C—H…X. The iodide anion in salt (1) is hydrogen bonded to three 4-[(2,2,2-trifluoroethoxy)methyl]pyridinium cations in the crystal packing, while the chloride ion in salt (2) is involved in six hydrogen bonds to five 4-[(2,2,2-trifluoroethoxy)methyl]pyridinium cations, which is attributed to the smaller size and reduced polarizability of the chloride ion compared to the iodide ion. In the IR spectra, the pyridinium N—H stretching band for salt (1) exhibited a blue shift compared with that of salt (2).