R0 Structural parameters, conformational, vibrational studies and ab initio calculations of cyanocyclopentane

The infrared and Raman spectra (3100-50 cm(-1)) of the gas, liquid or solution, and solid have been recorded of cyanocyclopentane, c-C5H9CN. Variable temperature (-60 to -100°C) studies of the infrared spectra (3100-400cm(-1)) of the sample dissolved in liquid xenon have been carried out. From these data, both the envelope-equatorial (Eq) and Ax conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 55 ± 12 cm(-1) (0.66 ± 0.14 kJ/mol) with the Eq conformer the more stable form. The percentage of the Ax conformer is estimated to be 45±1% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been made for the observed bands for both conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The r0 structural parameter values for the Eq[Ax] form are; for the heavy atom distances (Å): CN=1.160 [1.160] (3); Cα-C=1.463 [1.463] (3); Cα-Cβ, Cβ'=1.543 [1.545] (3); Cβ-Cγ, Cγ'=1.540 [1.541] (3); Cγ-Cγ'=1.552 [1.553] (3) and angles (°): ∠Cα-CN=179.0 [178.9] (5); ∠CβCα-C=113.1 [110.1] (5); ∠CβCαCβ'=103.0 [102.1] (5); ∠CαCβCγ=104.1 [104.8] (5); ∠CβCγCγ'=106.3 [106.0] (5). The results are discussed and compared to the corresponding properties of some related molecules.