Ortho-Substituent effect on the crystal packing and solid state speciation of aromatic C-nitroso compounds. Issue 30 (16th July 2020)

• Record Type: Journal Article
• Authors: Pike, Sarah J.; Heliot, Armelle; Seaton, Colin C.
• Is Part Of: CrystEngComm. Volume 22:Issue 30(2020)
• Page Start: 5040
• Page End: 5048
• Publication Date: 2020-07-16
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/d0ce00728e
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : The solid state behaviour of a short series aromatic C -nitroso compounds has been studied as a function of the electronic and steric nature of the ortho -substituent on the ring. Abstract : The solid state behaviour of a short series of aromatic C -nitroso compounds bearing a range of ortho -substituents, including amides, alcohols, methyl and fluorine have been investigated using single crystal X-ray diffraction. Solid state analysis has confirmed the contrasting speciation behaviour of aromatic C -nitroso compounds incorporating strongly and weakly electron-donating groups at the ortho -position with the former group adopting monomers or oxo-oxime tautomers whilst the latter group adopts either the cis - or trans -azodioxy dimer depending on the nature of the solvent employed in the crystallisation conditions. The presence of weakly electron-withdrawing fluorine substituents on the nitrosoarene leads to the formation of the trans -azodioxy dimer. Single crystal X-ray diffraction analysis has identified the presence of a diverse array of hydrogen-bonding interactions and π–π stacking interactions that support the adoption of a range of supramolecular aggregates, including chains and tunnels, in the crystal packing of this small library of aromatic C -nitroso compounds.