Rotational spectrum and structure of the pyridine–CO2 van der Waals complex

The rotational spectrum of the pyridine–CO2 van der Waals complex has been recorded in a cold supersonic jet using pulsed-nozzle Fourier transform microwave spectroscopy. Spectroscopic constants are reported for the parent species and for all four singly-substituted 13C derivatives. The data indicate a planar structure in which the pyridine nitrogen approaches the CO2 carbon with the C2 axis of the pyridine perpendicular to the CO2. No evidence of internal rotation is observed. The zero point vibrationally averaged N⋯C van der Waals distance is 2.7977(64) Å and the O⋯ortho-hydrogen distance is 3.090(6) Å. The 14N nuclear quadrupole coupling constants are consistent with a bending vibrational amplitude of the pyridine moiety of about 9° away from the C2v geometry. The observed structure is in excellent agreement with that previously calculated to correspond to the lowest of several nearly isoenergetic isomers, suggesting that it is, indeed, the global minimum-energy structure. Somewhat surprisingly, the C⋯N van der Waals bond distance is about 0.2 Å shorter than those observed in the related systems HCN⋯CO2 and H3N⋯CO2.

► The pyridine–CO2 van der Waals has a planar, C2v geometry. ► The pyridine nitrogen approaches the CO2 carbon with a 2.798 Å weak bond distance. ► No evidence of internal rotation is observed. ► The N⋯C distance is a 0.2 Å shorter than that in T-shaped HCN–CO2 and H3N–CO2.