Experimental and computational evidence for stabilising parallel, offset π[C(=O)N(H)N=C]⋯π(phenyl) interactions in acetohydrazide derivatives

Parallel, off-set π[C(=O)N(H)N=C] …π(phenyl) interactions are observed in the crystal of (2-thienyl)CH2CON(H)-N=C(H)Ph, along with more conventional non-covalent interactions. All notable interactions have been analysed by the calculated Hirshfeld surfaces, NCI plots and QTAIM analysis. The π[C(=O...

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Bibliographic Details
Main Authors: Tan, Sang Loon *, Cardoso, Laura N. F., Souza, Marcus V. N. de, Wardell, Solange M. S. V., Wardell, James L., Tiekink, Edward R. T. *
Format: Article
Language:English
Published: Royal Society of Chemistry 2022
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Online Access:http://eprints.sunway.edu.my/1956/
http://eprints.sunway.edu.my/1956/1/Tiekink%20crystengcomm%202022%2024%20962_acc.pdf
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Summary:Parallel, off-set π[C(=O)N(H)N=C] …π(phenyl) interactions are observed in the crystal of (2-thienyl)CH2CON(H)-N=C(H)Ph, along with more conventional non-covalent interactions. All notable interactions have been analysed by the calculated Hirshfeld surfaces, NCI plots and QTAIM analysis. The π[C(=O)N(H)N=C]…π(phenyl) interactions, whereby the N(H) atom lies over the ring centroid and with the N and C atoms on either side of the N(H) atom closely overlay 1,3-carbon atoms of the phenyl ring, are shown to be attractive. Theory suggests the energy of association provided the π[C(=O)N(H)N=C]…π(phenyl) interaction to the molecular packing to be about 15 kJ/mol, a value similar to that provided by similarly orientated benzene 2 and pyridine rings. A survey of the literature of related structures suggests comparable interactions occur in approximately 5-6% of crystals where they can potentially occur.