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Weak Interactions in Distyrylpyrazine Derivatives

With methoxy groups

Four new methoxy-substituted derivatives of E,E-2,5-bis(2-phenylethenyl)pyrazine have been synthesized. The supramolecular structures of the resulting set of five polymorphs have been studied using single-crystal X-ray diffraction to gauge the influence of the position of the methoxy groups on the organization of the molecules in the solid state, as part of an attempt to dispense with the particular polymorphism of the parent compound. The crystal packing patterns were analyzed in terms of the two pyrazine-based synthons found in the parent compound's crystal structure, the pi(pyrazine)...pi(phenyl) stacking synthon, and the pyrazine hydrogen-bonded synthon, as well as in terms of weak intermolecular interactions such as CH...O, CH...N, and CH...pi. The analysis shows that the introduction of methoxy groups in positions other than only the para position of the peripheral benzene rings successfully switches off the two synthons seen in the parent compound and that the new compounds adopt other packing strategies, based on methoxy...methoxy and –OCH3...pi contacts. Polymorphism, however, remains.

Collas, A.; Bagrowska, I.; Aleksandrzak, K.; Zeller, M.; Blockhuys, F. Cryst. Growth Des. 2011, 11, 1299-1309.

With fluorine atoms

Three derivatives of E,E-1,4-bis[2-(2,3,4,5,6-pentafluorophenyl)ethenyl]benzene, two of which bear nitrogen atoms in the ethenyl spacers, while in a third the central benzene ring is replaced by a pyrazine moiety, have been synthesized. The supramolecular structures of the resulting set of four compounds have been studied using single-crystal X-ray diffraction to gauge the influence of the position of the nitrogen atoms on the organisation of the molecules in the solid state. The crystal packing patterns were analyzed in terms of intermolecular interactions involving the fluorine and nitrogen atoms, i.e., CH...F, F...F, F...pi and CH...N interactions. The analysis shows that in two of the three solid-state structures the main effect of the nitrogen atoms in an indirect one: they do not participate in intermolecular contacts themselves, but activate nearby hydrogen atoms and phenyl rings in fluorine synthons to form new interactions.

Collas, A.; De Borger, R.; Amanova, T.; Blockhuys, F. CrystEngComm 2011, 13, 702-710.

 
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