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)

Type
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)
Pagina inizio
  • 4418 (literal)
Pagina fine
  • 4429 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 14 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 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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