Author:
Knop Osvald,Westerhaus Wolfgang J.,Falk Michael
Abstract
This investigation deals with the effect of temperature, between 10 and 293 K, on the ir spectrum of the NH3D+ probe ion in polycrystalline NH4SnF3, NH4CuSO3, cubic (NH4)2SiF6, and (NH4)2SnCl6. The results lead to the following conclusions. At 10 K these crystals contain symmetrically trifurcated [Formula: see text] bonds, i.e. bonds in which the N—H orientation of maximum probability is on the threefold axis. With increasing temperature these bonds lose progressively their symmetrically-trifurcated character to become highly bent, highly dynamic [Formula: see text]•bonds, and the strength of the hydrogen-bonding interaction increases. This is reflected in the decrease of the ND stretching frequency of the probe ion with increasing temperature, which is the opposite of the behaviour observed with normal (i.e. essentially straight) [Formula: see text] bonds.Re-determination of the room-temperature crystal structure of NH4CuSO3 has confirmed the correctness of the structure reported previously by Nyberg and Kierkegaard.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
24 articles.
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