Microwave spectra, molecular geometries, and internal rotation of CH3 in N-methylimidazole⋯H2O and 2-methylimidazole⋯H2O Complexes

Abstract

Broadband microwave spectra have been recorded between 7.0 and 18.5 GHz for N-methylimidazole⋯H₂O and 2-methylimidazole⋯H₂O complexes. Each complex was generated by co-expansion of low concentrations of methylimidazole and H₂O in argon buffer gas. The rotational spectra of five isotopologues of each complex have been assigned and analysed to determine rotational constants (A₀, B₀, C₀), centrifugal distortion constants (D_J, D_JK) and parameters that describe the internal rotation of the CH₃ group. The results allow the determination of parameters in the (r₀) molecular geometry of each complex. H₂O is the hydrogen bond donor and the pyridinic nitrogen of imidazole is the hydrogen bond acceptor in each case. The ∠(O–H_b⋯N3) angles are 177(5)° and 166.3(28)° for N-methylimidazole⋯H₂O and 2-methylimidazole⋯H₂O respectively. These results are consistent with the presence of a weak electrostatic interaction between the oxygen atom of H₂O and the hydrogen atom (or CH₃ group) attached to the C2 carbon atom of imidazole, and with the results of density functional theory calculations. The (V₃) barrier to internal rotation of the CH₃ group within N-methylimidazole⋯H₂O is essentially unchanged from the value of this parameter for the N-methylimidazole monomer. The same parameter is significantly higher for the 2-methylimidazole⋯H₂O complex than for the 2-methylimidazole monomer as a consequence of the weak electrostatic interaction between the O atom and the CH₃ group of 2-methylimidazole.