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Dense Semi‐Clathrates at High Pressure: A Study of the Water– tert ‐Butylamine System
Author(s) -
GraneroGarcía Rubén,
Falenty Andrzej,
Fabbiani Francesca P. A.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605090
Subject(s) - hydrate , hydrogen bond , crystallization , butylamine , water of crystallization , materials science , chemical physics , hydrogen , thermodynamics , chemical engineering , molecule , chemistry , crystallography , inorganic chemistry , organic chemistry , amine gas treating , physics , engineering
In situ high‐pressure crystallization and diffraction techniques have been applied to obtain two very structurally distinct semi‐clathrates of the tert ‐butylamine–water system with hydration numbers 5.65 and 5.8, respectively, thereby considerably reducing a notable hydration gap between the monohydrate and the 7 1 / 4 ‐hydrate that results when crystallization space is explored by temperature alone. Both structures can be considered as an intriguing solid‐state example of hydrophobic hydration, in which the water network creates wide tert ‐butylamine‐filled channels stabilized by cross‐linking hydrogen bonds. The existence of interconnected channels might also add low hydration structures to a list of potential targets for hydrogen storage. A detailed analysis of the topology of host water and host–guest interactions is reported and extended to those of other hydrates of the compound. This analysis offers new insight into properties of the tert ‐butylamine–water system and provides some clues as to the occurrence of the sizable number of hydrates of this compound.