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

CrystEngComm Pub Date: 2021-12-10 DOI: 10.1039/D1CE01492G

Abstract

Parallel, offset π[C([double bond, length as m-dash]O)N(H)N[double bond, length as m-dash]C]?π(phenyl) interactions are observed in the crystal of (2-thienyl)CH2CON(H)–N[double bond, length as m-dash]C(H)Ph, along with more conventional non-covalent interactions. All notable interactions were analysed using Hirshfeld surface analysis, NCI plots and QTAIM analysis. The π[C([double bond, length as m-dash]O)N(H)N[double bond, length as m-dash]C]?π(phenyl) interactions, whereby the [N with combining low line](H) atom lies over the ring centroid and the N and C atoms on either side of the [N with combining low line](H) atom closely overlay the 1,3-carbon atoms of the phenyl ring, are shown to be attractive. Theory suggests the energy of association provided by the π[C([double bond, length as m-dash]O)N(H)N[double bond, length as m-dash]C]?π(phenyl) interaction to the molecular packing to be about 15 kJ mol?1, a value similar to that provided by similarly oriented benzene and pyridine rings. A survey of related structures in the literature suggests that comparable interactions occur in approximately 5–6% of crystals where they can potentially occur.

Graphical abstract: Experimental and computational evidence for stabilising parallel, offset π[C( [[double bond, length as m-dash]] O)N(H)N [[double bond, length as m-dash]] C]?π(phenyl) interactions in acetohydrazide derivatives
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