Ionic Clathrate Hydrates of Tetra-n-Butylammonium Nitrate (TBANO3) and Mixed TBA(NO3,OH): Novel Superstructures of Tetragonal Structure I
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The structures of an ionic clathrate hydrate of tetra-n-butylammonium nitrate TBANO3·26.7H2O and mixed TBA(NO3)1−x(OH)x·(31.5 − x)H2O hydrate obtained from a mixture of tetra-n-butylammonium nitrate and tetra-n-butylammonium hydroxide are determined by single crystal X-ray diffraction. These structures are new types of superstructures based on classical tetragonal structure I with four- and twofold unit cells volumes for TBANO3·26.7H2O and TBA(NO3)1−x(OH)x·(31.5 − x)H2O respectively. The superstructures form as a result of ordering in the arrangement of multicompartment cavities of the water-anionic framework. A TBA cation is displaced from the center of combined cavities due to the anisotropic environment of the anions, which leads to an additional symmetry reduction. The modes of the nitrate anion incorporation into the water framework of ionic clathrate hydrates are determined for the first time.
Keywordsionic clathrate hydrates tetra-n-butylammonium nitrate tetra-n-butylammonium hydroxide structures X-ray crystallographic analysis disordered structures local ordering
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The authors are grateful to N. V. Kuratieva, A. I. Smolentsev, and B. S. Smolyakov for their assistance at different stages of the experimental work, and also to Prof. J. Lipkowski for discussing the results of the X-ray crystallographic analysis.
The work was supported by the State Contract of the Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences for basic scientific research.
Conflict of Interests
The authors declare that they have no conflict of interests.
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