Competition between H···π and H···O interactions in furan heterodimers

Here the interactions of furan with HZ (Z = CCH, CCF, CN, Cl, and F) are studied using a variety of electron correlation methods (MP2, CCSD(T), DFT-SAPT) and correlation-consistent triple- and quadruple-ζ basis sets including complete basis set (CBS) extrapolation. For Fu-HF all methods agree that a n-type structure with a hydrogen bridge between the oxygen lone-pair of furan and the hydrogen atom of HF is the global minimum structure. It is found to be significantly more stable than a π-type structure where the hydrogen atom of HF points toward the π system of furan. For the other four dimers MP2 and DFT-SAPT predict the π-type structure to be somewhat more stable, while CCSD(T) favors the n-type structure as the global minimum for Fu-HCl and predicts both structures as nearly isoenergetic for Fu-HCCH and Fu-HCCF. From a geometrical point of view, the Fu-HCN dimer structures are more related to those of the Fu-HCl complex than to Fu-HCCH. The different behavior of HCCF and HF upon complexation with furan evidence the effect of the presence of a π system in the aggregation of fluorine derivatives. It is shown that aggregates of furan cannot be understood by means of dipole-dipole and electrostatic analysis only. Yet, through a combined and detailed analysis of DFT-SAPT energy contributions and resonance effects on the molecular charge distributions a consistent explanation of the aggregation of furan with both π electron rich molecules and halogen hydrides is provided.