Rotational spectroscopy and molecular structure of the 1,1,2-trifluoroethylene-acetylene complex.

Helen O Leung, Mark D Marshall, Winn T Cashion, Vincent L Chen

Index: J. Chem. Phys. 128(6) , 064315, (2008)

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Abstract

Guided by ab initio calculations, Fourier transform microwave rotational spectra in the 6-22 GHz region are obtained for the complex formed between 1,1,2-trifluoroethylene and acetylene, including the normal isotopomer, three of four singly substituted (13)C species obtained in natural abundance, and using commercially available isotopic varieties of acetylene, species containing HCCD and H(13)C(13)CH. Although the ab initio calculations suggest two possible low energy planar arrangements for the molecules in the complex, only a single, unique structure is obtained from a combined analysis of the rotational constants derived from the spectra and atomic positions determined using Kraitchman [Am. J. Phys. 21, 17 (1953)] substitution coordinates. This structure is similar to that obtained for the CF(2)CHF[Single Bond]HF complex [H. O. Leung and M. D. Marshall, J. Chem. Phys. 126, 114310 (2007)] in which both the primary and secondary interactions occur between the HCCH molecule and a F atom and a H atom bonded to the same carbon of CF(2)CHF. The 2.748(15) A hydrogen bond has acetylene as the donor and 1,1,2-trifluoroethylene as the acceptor and forms a 104.49(15) degrees C[Single Bond]Fcdots, three dots, centeredH angle. The 2.8694(9) A secondary interaction between the pi bond of acetylene and the H atom geminal to the acceptor F atom causes the hydrogen bond to deviate 69.24(67) degrees from linearity. This large deviation from linearity and the similarity of the two intermolecular bond lengths suggest that the two interactions are becoming comparable in importance.