Microwave spectrum and molecular structure of the 1-chloro-1-fluoroethylene-hydrogen fluoride complex

Abstract

Guided by ab initio calculations, Fourier transform microwave spectra in the 8–22 GHz region are obtained for six isotopomers of the complex formed between 1-chloro-1-fluoroethylene and hydrogen fluoride. These include both 35Cl- and 37Cl-containing CH 2CClF with HF and DF, as well as 13CH 2C 35ClF and CH 2 13C 35ClF with HF. Analysis of the spectra determines the rotational constants, the complete chlorine quadrupole hyperfine coupling tensors in both the inertial and principal electric field gradient axis systems, and where appropriate, the diagonal components of the deuterium quadrupole coupling tensors. Spin–spin hyperfine structure is resolved and analyzed for CH 2C 35ClF–HF and CH 2C 37ClF–HF. The inertial information contained in the rotational constants combined with the HF and DF hyperfine interaction constants provides the structure for CH 2CClF–HF: a primary, hydrogen bonding interaction existing between the HF donor and the F atom acceptor on the 1-chloro-1-fluoroethylene moiety, while a secondary interaction occurs between the fluorine atom on the HF molecule and the H atom cis to the hydrogen-bonded F atom on the substituted ethylene, which causes the hydrogen bond to deviate from linearity. This is analogous to the structure obtained for 1-chloro-1-fluoroethylene-acetylene [H.O. Leung, M.D. Marshall, D.D. Grimes, J. Chem. Phys. 134 (2011) 034303] and similar to that of 1,1-difluoroethylene–HF [H.O. Leung, M.D. Marshall, T.L. Drake, T. Pudlik, N. Savji, D.W. McCune, J. Chem. Phys. 131 (2009) 204301], and indeed as with the acetylene complexes, to within experimental uncertainty, the intermolecular interactions in CH 2CClF–HF and its 1,1-difluoroethylene counterpart are practically indistinguishable.