Do the N-H...F and S-H...F Interactions Fnfluence on C-H...N and C-H...S Hydrogen Bonds?

Małgorzata Domagała ,  Sławomir J. Grabowski 

University of Łódź, Department of Crystallography and Crystal Chemistry (UŁ), Pomorska 149/153, Łódź 90-236, Poland

Abstract

We have found weak C-H...S and C-H...N hydrogen bonds in crystal structures of 1,3-thiazolidine derivatives, which we investigated both experimentally as well as theoretically [1, 2]. To get deeper insight into the nature of such interactions, we performed additional studies on simple modeling complexes [3]. Molecules of CH4, C2H4 and C2H2 were selected as proton donors and NH3 and H2S molecules were selected as acceptors. We carried out ab initio calculations (SCF, MP2) using different basis set, up to MP2/aug-cc-pVQZ//MP2/aug-cc-pVDZ level of approximation. We used MP2/6-311++G(d,p) and MP2/aug-cc-pVDZ wave functions in order to find and to characterize BCPs in terms of electron densities and their Laplacians. The Bader Theory [4] was applied for such analysis.

The aim of this work was the investigation of the complexes of fluorine derivatives of previously cited methane, ethene and acetylene with the ammonia and hydrogen sulfide molecules.

Rysunek4.jpg

Molecular graphs for the complexes C2H2F2 with H2S and C2H2F2 with NH3, respectively.

We were wonder if the same tendencies as before are in force here, i.e. if the hybridization effect is also observed [3, 6] and if similarly as for C(sp3)-H...O interactions the blue-shifting H-bonds are observed for C(sp3)-H...Y (Y=N, S) [5, 6].

However in same cases formation of N-H...F and S-H...F interactions occurs and it is of interest whether thay can affect the strength or geometrical parameters of earlier discussed C-H...N and C-H...S hydrogen bonds.

[1] M. Domagała, S. J. Grabowski, K. Urbaniak, G. Mlostoń, J. Phys. Chem. A 2003, 107, 2730.

[2] M. Domagała, S. J. Grabowski, K. Urbaniak, G. Mlostoń, J. Mol. Struct. 2004, 690, 69.

[3] M. Domagała, S. J. Grabowski, J. Phys. Chem. A 2005, 109, 5683.

[4] R. F. W. Bader, Chem. Rev. 1991, 91, 893.

[5] G. R. Desiraju, T. Steiner, The weak hydrogen bond in structural chemistry and biology, Oxford University Press Inc., New York, 1999.

[6] S. Scheiner, S. J. Grabowski, T. Kar, J. Phys. Chem. A 2001, 105, 10607.

Support have been provided by grant No. 505/675 2005 (University of Łódź). Use of computational resources of the Cracow Supercomputing Center is also acknowledged (grant No KBN/SGI2800/UŁódzki/082/2002).

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Presentation: poster at 18th Conference on Physical Organic Chemistry, Posters, by Małgorzata Domagała
See On-line Journal of 18th Conference on Physical Organic Chemistry

Submitted: 2006-05-31 09:40
Revised:   2009-06-07 00:44
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