The molecular structure and conformation of trichloronitromethane as determined by gas-phase electron diffraction and theoretical calculations

The molecular structure of trichloronitromethane has been studied in the gas phase using electron diffraction data. The molecules are found to undergo low barrier rotation about the CN bond with a planar CNO2 moiety in agreement with HF/MP2/B3LYP/6-311G(d,p) calculations. The experimental data are consistent with a dynamic model using a potential function for the torsion of V = (V6/2)(1 − cos 6τ). The major geometrical parameters (rg and ∠α) for the eclipsed form, obtained from least squares analysis of the data are as follows: r(NO3) = r(NO4) = 1.213(2) Å, r(CN) = 1.592(6) Å, r(CCl)av = 1.749(1) Å, ∠Cl5CN/∠Cl6CN = 109. 6°/106.3°(2), ∠O3NC/∠O4NC = 117. 6°/114.1°(4), τCl5C1N2O3 = 0.0°, and V6 = 0.20(25) kcal/mol.