2,1,3-Benzothiadiazole: Study of its structure, energetics and aromaticity

The present work reports an experimental study on the energetics of 2,1,3-benzothiadiazole and a computational study on its structure, energetics and aromaticity. In the experimental part the standard (p° = 0.1 MPa) massic energy of combustion, at T = 298.15 K, was measured by rotating bomb combustion calorimetry, in oxygen, and allowed the calculation of the respective standard molar enthalpy of formation, in the crystalline phase, at T = 298.15 K. The standard molar enthalpy of sublimation, at T = 298.15 K, was measured by high-temperature Calvet microcalorimetry. From the combination of data obtained by both techniques we were able to calculate the respective standard molar enthalpy of formation, in the gas phase, at T = 298.15 K: (276.6 ± 2.5) kJ · mol−1. This thermochemical parameter was compared with estimates obtained from high level ab initio quantum chemical calculations using the G3(MP2)//B3LYP composite method and various appropriately chosen reactions. The molecular structure of 2,1,3-benzothiadiazole was obtained from DFT calculations with the B3LYP density functional and various basis sets: 6-31G(d), 6-311(d,p), 6-311+G(3df,2p), aug-ccpVTZ and aug-ccpVQZ and its aromaticity and that of some related molecules were evaluated by analysis of nucleus independent chemical shifts (NICS) values.

► Enthalpies of formation of 2,1,3-benzothiadiazole were determined. ► The structure of 2,1,3-benzothiadiazole was obtained from DFT calculations. ► Calculations allowed estimation of enthalpy of formation in gas phase. ► The aromaticity was evaluated by analysis of NICS values.