http://www.cnr.it/ontology/cnr/individuo/prodotto/ID283666
Single N-C Bond Becomes Shorter than a Formally Double N=C Bond in a Thiazete-1,1-dioxide Crystal: An Experimental and Theoretical Study of Strong Crystal Field Effects (Articolo in rivista)
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- Label
- Single N-C Bond Becomes Shorter than a Formally Double N=C Bond in a Thiazete-1,1-dioxide Crystal: An Experimental and Theoretical Study of Strong Crystal Field Effects (Articolo in rivista) (literal)
- Anno
- 2014-01-01T00:00:00+01:00 (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
- 10.1021/cg500518a (literal)
- Alternative label
Leonardo Lo Presti, Ahmed M. Orlando, Laura Loconte, Riccardo Destro,
Emanuele Ortoleva, Raffaella SOAVE, Carlo Gatti (2014)
Single N-C Bond Becomes Shorter than a Formally Double N=C Bond in a Thiazete-1,1-dioxide Crystal: An Experimental and Theoretical Study of Strong Crystal Field Effects
in Crystal growth & design
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- Leonardo Lo Presti, Ahmed M. Orlando, Laura Loconte, Riccardo Destro,
Emanuele Ortoleva, Raffaella SOAVE, Carlo Gatti (literal)
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- Rivista
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- Universita? degli Studi di Milano, Department of Chemistry, Via Golgi 19, I-20133 Milano, Italy
Centre for Materials Crystallography, Århus University, Langelandsgade 140, DK-8000 Århus C, Denmark
Istituto di Scienze e Tecnologie Molecolari, Italian CNR, Via Golgi 19, I-20133 Milano, Italy (literal)
- Titolo
- Single N-C Bond Becomes Shorter than a Formally Double N=C Bond in a Thiazete-1,1-dioxide Crystal: An Experimental and Theoretical Study of Strong Crystal Field Effects (literal)
- Abstract
- 3-Diethylamino-4-(4-methoxyphenyl)-1,1-dioxo-
4H-1?6,2-thiazete-4-carbonitrile (DTC) is a synthetic compound
that exhibits a significant similarity with ?-sultamic drugs. Its core
chemical moiety is an uncommon four-membered thiazete-1,1-
dioxide heterocycle. Former crystallographic investigations carried
out at room temperature on different DTC polymorphs and a
chemically related compound showed a very unusual structural
feature: within the conjugated -N-C=N-SO2- system, the
formally single N-C bond is, on average, 0.018 Å shorter than the
formally double N=C bond. In this work, the charge density
distribution of DTC has been explored by both single-crystal X-ray
diffraction at T = 100(2) K and quantum mechanical simulations, with the aim of gaining insights into the subtle interplay
between structure, electron delocalization, and crystal field polarization effects. To this end, both local and nonlocal topological
descriptors provided by the Quantum Theory of Atoms in Molecules have been employed. Topological and structural changes of
crystalline and in vacuo DTC have been related to the smaller or larger importance of resonance forms in the -N-C=N-SO2-
moiety. A rationale for the mentioned C-N/C=N bond length inversion is found in terms of the large DTC dipole moment
enhancement occurring in the crystal, which stabilizes highly polar resonant forms that exploit more favorable electrostatic
interactions with neighboring molecules. In turn, this causes a significant electronic rearrangement within the molecule that
results in an unusual and counterintuitive bond length alternation pattern. Possible implications from the viewpoint of the
accurate in silico modeling of crystal structures are discussed (literal)
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