6,6'-Dimethyl-1,1',5,5'-tetraaza-6,6'-bi(bicyclo[3.1.0]hexane): synthesis and investigation of molecular structure by quantum-chemical calculations, NMR spectroscopy and X-ray diffraction analysis
| Autor: | I. N. Kolesnikova, Alexander S. Goloveshkin, Vladimir V. Kuznetsov, Nina N. Makhova, Nikolai Andreevich Chegodaev, Igor F. Shishkov |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_compound
Crystallography Bicyclic molecule Diaziridine Chemistry Atoms in molecules Molecule Nuclear magnetic resonance spectroscopy Physical and Theoretical Chemistry Condensed Matter Physics Conformational isomerism Two-dimensional nuclear magnetic resonance spectroscopy Natural bond orbital |
| Popis: | A new diaziridine derivative with two bicyclic diaziridine-containing moieties in one molecule, 6,6'dimethyl-1,1',5,5'-tetraaza-6,6'-bi(bicyclo[3.1.0]hexane) (BiDiMDAH), has been synthesized for the first time. Its molecular structure has been investigated in the gas phase by means of quantum-chemical (QC) calculations, in CDCl3 solution by 1D and 2D NMR spectroscopy and in the solid state by the X-ray diffraction (XRD) technique. It was found by QC calculations that BiDiMDAH molecule in a free state presents a single conformer of C2 symmetry with trans orientation of the of the methyl groups about two carbons connecting diaziridine cycles. The 5-memebered rings in BiDiMDAH molecule has been found to be essentially planar. In order to explain conformational preferences of BiDiMDAH Natural Bond Orbitals (NBO) and Atoms in Molecules (AIM) analyses have been performed. According to the XRD data BiDiMDAH crystallizes in space group P21/c with molecular structure similar to that obtained by the means of QC calculations. The data of NMR spectroscopy has revealed that only one conformer is present in CDCl3 solution in agreement with the data of QC and XRD studies. The gaseous standard enthalpy of formation of BiDiMDAH has been estimated to be 443.8 ± 5.0 kJ/mol by means of G4 theory. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|