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π-Hole interactions at work: crystal engineering with nitro-derivatives

Authors: Antonio Bauza; Anastasiya V. Sharko; Ganna Senchyk; Eduard B. Rusanov; Antonio Frontera; Konstantin V. Domasevitch

Publication Date: -0001-11-30  Article ASAP

In this manuscript we report the design, synthesis and X-ray characterization of nitrodiene derivatives that present crucial π-hole interactions involving the nitro group as π-hole donor. Solid state structures of 1,4-dinitro-1,3-butadiene (1), its co-crystal 1Diox and homologous 1,4-dinitro-1,3-pentadiene (2) and 2,4-dinitro-2,4-hexadiene (3) feature competition of the latters with common weak CHO bonding and gradually increased role of lone pair- π-hole NO2NO2 interactions. Regular evolution of the supramolecular patterns (1 to 3) results in generation of unprecedented 3D non-covalent framework in 3 that is controlled exclusively by short π-hole contacts (O•••N = 2.9615(18), 3.1304(18) Å). These findings complement results of high level ab initio calculations (MP2/def2-TZVP) and unite theory and experiment thus supporting the functional relevance of this novel π-hole interaction.  Read more