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Polymorphism in secondary squaramides: on the importance of π-interactions involving the four membered ring

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We report the X-ray solid state structures of four new squaric acid derivatives, i.e. three polymorphs of 3,4-bisIJ(2-(dimethylamino)ethyl)amino)cyclobut-3-ene-1,2-dione (1a-c) and a co-crystal of compound 1 and resorcinol (2). All structures form interesting supramolecular assemblies in the solid state which have been analyzed using high level DFT calculations and molecular electrostatic potential (MEP) surface calculations. A combination of H-bonding and π-π stacking interactions of the cyclobutenedione rings are crucial for the formation of the supramolecular assemblies in the solid state. Moreover, unusual antiparallel CO⋯CO interactions observed in the X-ray structure of one of the polymorphs of 1 and the lp-π interactions between one oxygen atom of resorcinol and the squaramide ring in 2 have been characterized using Bader's theory of 'atoms-in-molecules' (AIM).

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PROHENS LÓPEZ, Rafael, PORTELL BUESO, Anna, VALLCORBA, Oriol, FONT BARDIA, Ma. mercedes, BAUZÁ, Antonio, FRONTERA, Antonio. Polymorphism in secondary squaramides: on the importance of π-interactions involving the four membered ring. _Crystengcomm_. 2018. Vol. 20, núm. 2, pàgs. 237-244. [consulta: 24 de gener de 2026]. ISSN: 1466-8033. [Disponible a: https://hdl.handle.net/2445/163123]

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