1. The 1 : 1 and 1 : 2 salts of 1,4-diazabicyclo[2.2.2]octane and bis(trifluoromethylsulfonyl)amine: thermal behaviour and polymorphism.
- Author
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Gerhard Laus, Michael Hummel, Daniel M. Többens, Thomas Gelbrich, Volker Kahlenberg, Klaus Wurst, Ulrich J. Griesser, and Herwig Schottenberger
- Subjects
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AMINES , *THERMAL analysis , *POLYMORPHISM (Crystallography) , *STOICHIOMETRY , *X-ray diffraction , *HIGH temperatures , *ENANTIOMERS , *INTERMEDIATES (Chemistry) , *MOLECULAR structure , *HYDROGEN bonding - Abstract
The salts of 1,4-diazabicyclo[2.2.2]octane (DABCO) and bis(trifluoromethylsulfonyl)amine (in 1 : 1 and 1 : 2 stoichiometry, 1and 2, respectively) were investigated by DSC, TGA, PXRD and single crystal X-ray diffraction. Thermal analysis of the two compounds revealed reversible phase transitions, indicating enantiotropic relationships between all the polymorphs. Compound 1can exist as a room-temperature form 1Land as a high-temperature modification 1H. By contrast, 2forms a low- (2L), an intermediate- (2I) and a high-temperature (2H) polymorph. The structures of 1Land 2Lwere determined by single crystal X-ray crystallography. N–HO bonded cations of 1Lare arranged in a staggered fashion and form infinite chains. The crystal contains two sets of symmetry related H-bonded chains, which are in an inclined orientation relative to one another. In the structure of 2L, the cation is N–HO bonded to two neighbouring triflimide anions. The discrete H-bonded structure fragments resulting from these interactions assemble to a layer structure. The structure determination of the high-temperature forms 1Hand 2Hfrom PXRD data was negatively affected by a high degree of disorder of the triflimide anions. All N–HO bonded DABCO chains in 1Hadopt a parallel orientation, which is in contrast to the inclined orientation found in 1L. [ABSTRACT FROM AUTHOR]
- Published
- 2011
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