Tetranitromethan – ein Albtraum molekularer Flexibilität in Gasphase und Festkörper

Vishnevskiy, Yury V.; Tikhonov, Denis S.; Schwabedissen, Jan; Stammler, Hans‐Georg; Moll, Richard; Krumm, Burkhard; Klapötke, Thomas M.; Mitzel, Norbert W.

doi:10.1002/ange.201704396

Cited by 7 publications

(4 citation statements)

References 33 publications

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“…Therefore, both conformers are interacting by pure O⋅⋅⋅O contacts. With regards to the (Cl3NM) 2 ‐ a dimer, there are two stable BCP between O and Cl atoms that are not related to classical σ‐hole halogen bonds, in line with the experimental results of Politzer et al [55] . They found out that the entire surface of chlorine is rather positive.…”

Section: Resultssupporting

confidence: 85%

“…In this section we further analyzed the presence of intermolecular O⋅⋅⋅O interactions within more realistic environments. For instance, tetranitromethane [55] (4NM, refcode ZZZWEW) is liquid at room temperature (m. p. 13–14 °C, b. p. 126 °C), and due to its molecular structure short contacts between oxygen atoms must be present. We therefore took this molecule as a model compound to explore the presence of intermolecular O⋅⋅⋅O interactions between nitro groups.…”

Section: Resultsmentioning

confidence: 99%

“…Despite the large number of studies carried out, there is still no consistent description. By applying a 4D dynamic model for the treatment of data obtained by gas‐phase electron diffraction, these authors described the extremely dynamic behavior of 4NM in this phase [55] . They also state that “all quantum‐chemical calculations predicted S 4 symmetry for the ground state and no other conformational minima.…”

Section: Resultsmentioning

confidence: 99%

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Nature and Strength of Weak O⋅⋅⋅O Interactions in Nitryl Halide Dimers

2023

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The use of real space functions and molecular graphs has pushed some chemists to wonder: Are interactions between negatively charged oxygen atoms possible? In this contribution we analyze whether there is a real interaction between oxygen atoms in nitryl halide dimers (XNO 2 ) 2 (X = F, Cl, Br and I) and in tetranitromethane and derivatives. Based on ab-initio and density functional theories (DFT) methods, we show these complexes are weakly stabilized. Energy decomposition analyses based on local molecular orbitals (LMOEDA) and interacting quantum atoms (IQA) reveal both dispersion and exchange play a crucial role in the stabilization of these complexes. Electron charge density and IQA analyses indicate that the oxygen atoms are connected by privileged exchange channels. In addition, electrostatic interactions between O and N atoms are also vital for the stabilization of the complexes. Finally, a reasonable explanation is given for the dynamic behavior of nitryl groups in tetranitromethane and derivatives.

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Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Nature and Strength of Weak O⋅⋅⋅O Interactions in Nitryl Halide Dimers

2023

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“…[a] Professor Dr Alexander J. Part of the appeal of the Communication by Mitzel et al [9] lies in the resolution of many decades of uncertainty over the true structure of tetranitromethane. Allied to this are the shortcomings or apparently incompatible results of earlier studies, including those using GED [10a, b] , infrared and Raman spectroscopies [10c] and SCXRD [10d] .…”

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confidence: 99%

Structure Determination Techniques Flex Their Muscles

Blake

2017

Angew Chem Int Ed

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Gas-phase electron diffraction (GED) has been around since 1928 [1] , providing invaluable information about the structures of small molecules. Because the structural information is unaffected by interactions between neighbouring molecules, as seen to various degrees in the solid state, it can more readily be compared to the results of ab initio theoretical calculations. As a result, GED provides reliable structures against which the results of theoretical calculations can be validated, while calculations can help to resolve structural features which are not well represented in the GED data [2] .The GED technique ( Figure 1) has undergone significant development since its inception, both experimentally and theoretically, with the result that it has delivered steadily more accurate and reliable structures. The technique is practiced by a small number of highly-experienced research groups, a reflection of both the challenges and limitations of the technique [3] . One of the major limitations is that GED data are effectively onedimensional, so that similar distances (bonded or non-bonded) overlap in the radial distribution function, such that the successful determination of more complex or difficult structures may depend on the availability of additional data from techniques such as ab initio calculations, X-ray crystallography, liquid crystal NMR spectroscopy, or rotational spectroscopy [4] . Structure analysis by single crystal X-ray diffraction (SCXRD) has an even longer pedigree. Ever since the first crystal structure determination was published in 1913, the technique has been at the forefront of many of the most important scientific developments of the past century [5] and is a standard characterisation technique for new materials and for investigating structural variability: the Cambridge Structural Database of smallmolecule crystal structures [6] alone now contains around 900,000 entries. The method does have its limitations, the most obvious being the requirement for -ideally -relatively large single crystals composed of unit cells with a consistent repetition of atomic positions. However, given suitable hardware, software, skill and time, considerable deviations from this ideal can be accommodated [7] . Another feature of structures determined by SCXRD is that molecules are in close proximity to each other, the effects of which can range from insignificant to extreme. The field of crystal engineering [8] , which involves the design, construction and analysis of crystal structures of organic and metal-organic compounds, is based on the existence of significant intermolecular interactions in the solid state.So, given the power and maturity of these techniques for structure determination, why is the successful determination of the structure of a simple molecule such as tetranitromethane (Figure 2a) in the gas-phase and the solid state such a big deal? [a] Professor Dr Alexander J. Part of the appeal of the Communication by Mitzel et al. [9] lies in the resolution of many decades of uncertainty over the t...

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Strukturbestimmungsmethoden zeigen ihre Stärke

Blake¹

2017

Angewandte Chemie

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Tetranitromethan – ein Albtraum molekularer Flexibilität in Gasphase und Festkörper

Cited by 7 publications

References 33 publications

Nature and Strength of Weak O⋅⋅⋅O Interactions in Nitryl Halide Dimers

Nature and Strength of Weak O⋅⋅⋅O Interactions in Nitryl Halide Dimers

Structure Determination Techniques Flex Their Muscles

Strukturbestimmungsmethoden zeigen ihre Stärke

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