A study of the H-bonded structures and infrared and Raman spectral analysis of carbohydrazide and thiocarbohydrazide

The complex conformational profile and the vibrational spectra of carbohydrazide (1,3-diaminourea) and thiocarbohydrazide were investigated by the DFT-B3LYP and ab initio MP2 and MP4(SDQ) levels of theory using the 6-311G** basis set. The planar syn-cis-anti-trans structure of the two molecules with Cs symmetry was predicted to have an imaginary frequency. The corresponding non-planar structure (C1 symmetry) was predicted to be the lowest energy structure and to have a positive real frequency as the real minima of the molecules. The stability of the non-planar structure agrees with the X-ray study of carbohydrazide where significant molecular distortions from planarity were reported for the lowest energy form as a result of strong intermolecular hydrogen bonding in the crystal. The vibrational wavenumbers of the lowest energy non-planar conformer of carbohydrazide and thiocarbohydrazide were computed at the B3LYP level and complete vibrational assignments were provided on the basis of the combined DFT-B3LYP results, normal coordinate calculations and experimental infrared and Raman data.

► The structure of carbohydrazide and thiocarbohydrazide is optimized at the DFT-B3LYP, MP2 and MP4(SDQ) levels.
► The optimized lowest energy structure of carbohydrazide was compared to the X-ray structure.
► The vibrational wavenumbers of the molecules were calculated at the DFT-B3LYP level.
► Vibrational assignments were provided by combining experimental infrared and Raman spectra and theoretical data.