X-ray structure, semi-empirical MO calculations and π-electron delocalization of 1-cyanoacetyl-5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazoles

The structure of three 1-cyanoacetyl-3-alkyl[aryl]-5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazoles (1–3) has been determined by X-ray diffractometry. The 4,5-dihydro-1H-pyrazole rings were obtained as almost planar structures showing RMS deviation at a range of 0.0196–0.0736 Å. The data demonstrate that the molecular packing is dependent on the substituent present in each molecule. In addition, a computational investigation using semi-empirical AM1 and RM1 methods was performed in order to investigate the correlation between experimental and calculated geometrical parameters. The data obtained suggest that the structural data furnished by the AM1 method is in better agreement with those experimentally determined for the above compounds. An analysis of the π-electron delocalization by HOMA calculations indicate that there is a hyperconjugation effect in the imine group toward to phenyl group at ring 3-position of compound 2, and that this resonance effect decrease in compounds 1 and 3. In addition, it was showed that bond N(1) and C(6) do not have an amide character. Thus, the O(6)–C(6)–N(1)–N(2)–C(3) fragment is not completely delocalized mainly due to the low π-electron delocalization in N(1)–N(2) bond for all compounds.