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Halogenotrinitromethanes: A Combined Study in the Crystalline and Gaseous Phase and Using Quantum Chemical Methods
Author(s) -
Klapötke Thomas M.,
Krumm Burkhard,
Moll Richard,
Rest Sebastian F.,
Vishnevskiy Yury V.,
Reuter Christian,
Stammler HansGeorg,
Mitzel Norbert W.
Publication year - 2014
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.201402798
Subject(s) - natural bond orbital , intramolecular force , intermolecular force , crystallography , molecule , chemistry , electron diffraction , atomic orbital , phase (matter) , hydrogen bond , bond length , single bond , atoms in molecules , diffraction , quantum chemical , computational chemistry , crystal structure , stereochemistry , electron , group (periodic table) , physics , organic chemistry , optics , quantum mechanics
The halogenotrinitromethanes FC(NO 2 ) 3 ( 1 ), BrC(NO 2 ) 3 ( 2 ), and IC(NO 2 ) 3 ( 3 ) were synthesized and fully characterized. The molecular structures of 1 – 3 were determined in the crystalline state by X‐ray diffraction, and gas‐phase structures of 1 and 2 were determined by electron diffraction. The HalC bond lengths in F, Cl, and BrC(NO 2 ) 3 in the crystalline state are similar to those in the gas phase. The obtained experimental data are interpreted in terms of Natural Bond Orbitals (NBO), Atoms in Molecules (AIM), and Interacting Quantum Atoms (IQA) theories. All halogenotrinitromethanes show various intra‐ and intermolecular non‐bonded interactions. Intramolecular N ⋅⋅⋅ O and Hal ⋅⋅⋅ O (Hal=F ( 1 ), Br ( 2 ), I ( 3 )) interactions, both competitors in terms of the orientation of the nitro groups by rotation about the CN bonds, lead to a propeller‐type twisting of these groups favoring the mentioned interactions. The origin of the unusually short HalC bonds is discussed in detail. The results of this study are compared to the molecular structure of ClC(NO 2 ) 3 and the respective interactions therein.