The role of the nitro group on the formation of intramolecular hydrogen bond in the methyl esters of 1-vinyl-nitro-pyrazolecarboxylic acids

•Synthesis of methyl esters of 1-vinyl-4(5)-nitro-pyrazolecarboxylic acids.•Analyses of formation of hydrogen bonds by XRD, NMR and QCC.•Intramolecular hydrogen bond =CH…O is formed in 5-substituted N-vinyl pyrazoles.•Nitro group can hinder or form hydrogen bond depending on its position in the ring. All reactions involving the nitrogen atom in 3(5)-substituted pyrazoles inevitably lead to a mixture of N-substituted 3- and 5- isomers due to tautomerism. The position of substituent can affect the behavior of N-vinyl isomers, in particular, the ability of some functional groups to form =CH…O or =CH…N weak hydrogen bonding type interaction with α-hydrogen of vinyl group due to steric reasons. Moreover, the additional substituents in the pyrazole ring can further influence the possibility and nature of specific intramolecular interactions. Here we have shown the effect of the nitro group on the formation of hydrogen bonds in methyl esters of 1-vinyl-4-nitro-3(5)- and 1-vinyl-5-nitro-3(5)-pyrazole carboxylic acids. A comprehensive study, including synthesis, quantum chemical calculations, NMR and XRD analysis, allowed to conclude that, contrary to expected, in the methyl ester of 1-vinyl-4-nitro-5-pyrazolecarboxylic acid, the formation of a planar conformation is unfavorable, preventing formation of a classical hydrogen bond. On the other hand, there is a hydrogen bond between the nitro group and vinyl group in 1-vinyl-5-nitro-pyrazolecarboxylic acids. [Display omitted]