Microwave Spectrum and Molecular Structure of Formamide

The microwave spectra of ten isotopic species of formamide (H2N–CHO) have been investigated. Type a and type b transitions have been identified and measured for all ten species. The inertial defect is found to decrease whenever a heavier isotope is substituted for any atom in the NH2 group, and in fact is negative for four of the species studied. It is concluded that the molecule is nonplanar with the H2N–C group forming a shallow pyramid. The structural parameters deduced from the rotational constants are: r(N–H′, where H′ is trans to the aldehyde hydrogen) = 1.014±0.005 A, r(N–H″, where H″ is cis to the aldehyde hydrogen) = 1.002±0.005 A, r(N–C) = 1.376±0.010 A, r(C–H) = 1.102±0.010 A, r(C=O) = 1.193±0.020 A, ∠H′NH″ = 118°53′ ±40′, ∠H″NC = 120°37′±40′, ∠H′NC = 117°9′±40′, ∠NCO = 123°48′±40′, ∠NCH = 113°14′±40′ and ∠OCH = 122°58′±40′. The dihedral angles between the H′NC plane and the NCO plane, and between the H″NC plane and the NCH plane, are 7°±5°, and 12°±5°, respectively. In all the spectra investigated each line was accompanied by a vibrational satellite line of anomalously high intensity. Measurements of relative intensities were carried out for H2N14–CHO, cis- and trans-HDN14–CHO, and D2N14–CHO. The energy levels (above the zero point) deduced from these measurements show a very large isotope shift, and are interpreted as being due to the first excited state of the NH2 wagging frequency. A pyramidal model for formamide will have two equilibrium configurations separated by a potential barrier. With a Manning type potential, a barrier of 370±50 cm−1, hindering the ``inversion-wagging'' type of motion, is determined. The equilibrium value of the normal coordinate calculated from the Manning potential is found to be in good agreement with that found in the structure determination.