Rotational spectroscopy and molecular structure of the 1,1-difluoroethylene-acetylene complex

Abstract

Fourier transform microwave, rotational spectra in the 6-21 GHz region are obtained for the complex formed between 1,1-difluoroethylene and acetylene, including the normal isotopomer and each singly substituted (13)C species along with complexes derived from commercially available isotopic varieties of acetylene (HCCD, DCCD, and H(13)C(13)CH). Although two possible planar structures are consistent with the rotational constants derived from analysis of the spectra, ab initio calculations, as well as chemical intuition, support only one of the two as the structure of the complex. Nuclear quadrupole coupling constants for D-containing species show no evidence of electric field gradient perturbation and are consistent with the structures obtained from inertial data. The primary interaction between the two molecules is a 2.646(11) A hydrogen bond with acetylene as the donor and a 1,1-difluoroethylene fluorine as the acceptor that forms a 122.41(79) degrees C-Fcdots, three dots, centeredH angle. A secondary interaction between the acetylenic bond and the difluoroethylene hydrogen atom cis to the acceptor fluorine atom causes the hydrogen bond to deviate 53.25(24) degrees from linearity. Structural comparisons with the related complex, 1,1-difluoroethylene-hydrogen chloride [Z. Kisiel et al., J. Chem. Soc., Faraday Trans. 88, 3385 (1992)], suggest that the hydrogen bond in the acetylene complex is weaker, whereas comparisons with vinyl fluoride-acetylene [G. C. Cole and A. C. Legon, Chem. Phys. Lett. 369, 31 (2003)] indicate that the fluorine atoms in 1,1-difluoroethylene are less basic than the one in vinyl fluoride.