A computational investigation of cooperativity in weakly hydrogen-bonded assemblies

Abstract

The non-covalent forces present in ethyne oligomers and ethyne–water aggregates containing C–H  · · ·  π(C[triple bond, length half m-dash]C) interactions, are investigated using ab initio calculations. The C–H  · · ·  π(C[triple bond, length half m-dash]C) interaction is found to be a very weak hydrogen bonding interaction, in accordance with previously reported work, with an enthalpy of interaction of around –4 kJ mol^–1. The potential surface of this interaction in the ethyne T-shaped dimer demonstrates that the interaction energy is relatively insensitive to the position of the donating proton along the bond vector of the accepting triple bond as well as to the tilt angle of the major axis of the acetylene molecule.

The strength of the O–H  · · ·  π(C[triple bond, length half m-dash]C) contact is found to be consistent with a very weak hydrogen bonding interaction with an enthalpy of interaction of around –6 kJ mol^–1 which is very similar to that of the ethyne T-shaped dimer although ethyne is a much poorer hydrogen bond donor. The interaction energy per C–H  · · ·  π(C[triple bond, length half m-dash]C) interaction in ethyne trimers, both cyclic and linear, as compared to that in the ethyne dimer does not appear to suggest that there are large gains in stabilisation through cooperativity and the use of a more polarised surface—that of a water molecule—to create larger polarisation effects again resulted in small cooperative gains (0–10% range) suggesting that hydrogen-bonded arrays containing terminal alkynes are incapable of exhibiting significant cooperative enhancements. It is demonstrated that the shifts in the stretching frequency of the C–H bond of propyne in different intermolecular C–H  · · ·  O hydrogen bonding environments are insignificant relative to the effects of the accepting strength of the oxygen and therefore infra-red spectroscopic data may not provide sufficient evidence to prove that large cooperative effects operate in these hydrogen bonding arrays.

References

1. (a) Z. Berkovitch-Yellin and L. Leiserowitz, Acta Crystallogr., Sect. B, 1984, 40, 159; (b) G. R. Desiraju, Acc. Chem. Res., 1996, 29, 441; (c) T. Steiner, Chem. Commun., 1997, 727.
2. (a) C. A. Hunter and J. K. M. Sanders, J. Am. Chem. Soc., 1990, 112, 5525; (b) C. A. Hunter, Chem. Soc. Rev., 1994, 23, 101; (c) D. R. Boyd, T. A. Evans, W. B. Jennings, J. F. Malone, W. O'Sullivan and A. Smith, Chem. Commun., 1996, 2269; (d) T. Steiner, S. A. Mason and M. Tamm, Acta Crystallogr., Sect. B, 1997, 53, 843.
3. (a) J. L. Atwood, F. Hamada, K. D. Robinson, G. W. Orr and R. L. Vincent, Nature, 1991, 349, 683; (b) S. Suzuki, P. G. Green, R. E. Bumgarner, S. Dasgupta, W. A. Goddard III and G. A. Blake, Science, 1992, 257, 942; (c) K. Subramanian, S. Lakshmi, K. Rajagopalan, G. Koellner and T. Steiner, J. Mol. Struct., 1996, 384, 121.
4. (a) N. Ramasubbu, R. Parthasarathy and P. Murray-Rust, J. Am. Chem. Soc., 1986, 108, 4308; (b) V. R. Pedireddi, D. S. Reddy, B. S. Gould, D. C. Craig, A. D. Rae and G. R. Desiraju, J. Chem. Soc., Perkin Trans. 2, 1994, 2353; (c) D. S. Reddy, D. C. Craig and G. R. Desiraju, J. Am. Chem. Soc., 1996, 118, 4090.
5. (a) G. R. Desiraju and A. Gavezzotti, Acta Crystallogr., Sect. B, 1989, 45, 473; (b) C. V. Sharma, K. Panneerselvam, T. Pilati and G. R. Desiraju, J. Chem. Soc., Perkin Trans. 2, 1993, 2209; (c) C. A. Hunter, J. Mol. Biol., 1993, 230, 1025.
6. (a) T. Steiner, J. Chem. Soc., Chem. Commun., 1995, 95; (b) M. Pilkington, J. D. Wallis and S. Larsen, J. Chem. Soc., Chem. Commun., 1995, 1499; (c) T. Steiner, E. B. Starikov, A. M. Amado and J. J. C. Trixeria-Dias, J. Chem. Soc., Perkin Trans. 2, 1995, 1321; (d) T. Steiner, M. Tamm, B. Lutz and J. van der Maas, Chem. Commun., 1996, 1127; (e) T. Steiner, E. G. Starikov and M. Tamm, J. Chem. Soc., Perkin Trans. 2, 1996, 67; (f) T. Steiner, M. Tamm, A. Grzegorzewski, N. Schulte, N. Veldman, A. M. M. Schreurs, J. A. Kanters, J. Kroon, J. van der Maas and B. Lutz, J. Chem. Soc., Perkin Trans. 2, 1996, 2441; (g) F. H. Allen, J. A. K. Howard, V. J. Hoy, G. R. Desiraju, D. S. Reddy and C. C. Wilson, J. Am. Chem. Soc., 1996, 118, 4081; (h) T. Steiner, B. Lutz, J. van der Maas, N. Veldman, A. M. M. Schreurs, J. Kroona and J. A. Kanters, Chem. Commun., 1997, 191; (i) T. Steiner, J. van der Maas and B. Lutz, J. Chem. Soc., Perkin Trans. 2, 1997, 1287.
7. (a) H.-C. Weiss, D. Bläser, R. Boese, B. M. Doughan and M. M. Haley, Chem. Commun., 1997, 1703; (b) J. M. A. Robinson, B. M. Kariuki, R. J. Gough, K. D. M. Harris and D. Philp, J. Solid State Chem., 1997, 134, 203.
8. G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997, pp. 103–107.
9. (a) G. A. Jeffrey, M. E. Gress and S. Takagi, J. Am. Chem. Soc., 1977, 99, 609; (b) W. Saenger, Nature, 1979, 279, 343; (c) G. A. Jeffrey and S. Takagi, Acc. Chem. Res., 1978, 11, 264; (d) G. A. Jeffrey and L. Lewis, Carbohydr. Res., 1978, 60, 179; (e) W. Saenger and K. Lindner, Angew. Chem., Int. Ed. Engl., 1980, 19, 398.
10. (a) Y. C. Tse and M. D. Newton, J. Am. Chem. Soc., 1977, 99, 611; (b) J. Elguero, O. Mó and M. Yáñez, J. Chem. Phys., 1992, 97, 6628; (c) M. Lozynski, H.-G. Mack and D. Rusinska-Roszak, J. Phys. Chem., 1997, 101, 1542.
11. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis and J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347 Version dated 22 November 1995 was used for all calculations.
12. CADPAC, The Cambridge Analytical Derivatives Package, Issue 6.1, Cambridge, 1996.
13. Wavefunction Inc., Irvine, CA, 1995, Version 4.1.1.
14. J. A. Pople, K. Raghavachari, H. B. Schlegel and J. S. Binkley, Int. J. Quant. Chem. Symp., 1979, 13, 225.
15. (a) S. F. Boys and F. Bernardi, Mol. Phys., 1970, 19, 553; (b) F. B. van Duijneveldt, J. G. C. M. van Duijneveldt-van de Rijdt and J. H. van Lenthe, Chem. Rev., 1994, 94, 1873.
16. M.-F. Fan, Z. Lin, J. E. McGrady and D. M. P. Mingos, J. Chem. Soc., Perkin Trans. 2, 1996, 563.
17. The TZ2P basis for C and H comprises the 5s3p and 3s contracted sets of Dunning (T. H. Dunning, J. Chem. Phys, 1971, 55, 716) augmented by polarisation functions: J. Gauss, J. F. Stanton and R. J. Bartlett, J. Chem. Phys., 1992, 97, 7825.
18. (a) I. L. Alberts, T. W. Rowlands and N. C. Handy, J. Chem. Phys., 1988, 88, 3811; (b) H. Petrusová, Z. Havlas, P. Hobza and R. Zahradník, Collect. Czech. Chem. Commun., 1988, 53, 2495; (c) R. G. A. Bone, C. W. Murray, R. D. Amos and N. C. Handy, Chem. Phys. Lett., 1989, 161, 166; (d) J. Yu, S. Su and J. E. Bloor, J. Phys. Chem., 1990, 94, 5589; (e) P. Hobza, H. L. Selzle and E. W. Schlag, Collect. Czech. Chem. Commun., 1992, 57, 1187.
19. F. H. Allen and O. Kennard, Chemical Design and Automation News, 1993, 8, pp. 1, 31–37 The search criteria (CSD version 5.14 released October 1997) were error and disorder free organic only structures with R factors less than 10%.
20. R. Taylor and O. Kennard, Acc. Chem. Res., 1984, 17, 320.
21. (a) R. Taylor, J. Mol. Struct., 1981, 73, 125; (b) H. Umeyama and K. Morokuma, J. Am. Chem. Soc., 1997, 99, 1316.
22. D. G. Prichard, R. N. Nandi and J. S. Muenter, J. Chem. Phys., 1988, 89, 115.
23. J. S. Craw, M. A. C. Nascimento and M. N. Ramos, Spectrochim. Acta, Part A, 1991, 47, 69.
24. L. Turi and J. J. Dannenberg, J. Phys. Chem., 1993, 97, 7899.
25. M. Pilkington, J. D. Wallis and S. Larsen, J. Chem. Soc., Chem. Commun., 1995, 1499.
26. A. C. Legon and D. J. Millen, Chem. Soc. Rev., 1992, 21, 71.
27. (a) D. Hankins, J. N. Moskowitz and F. H. Stillinger, J. Chem. Phys., 1970, 53, 4544; (b) G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford University Press, New York, 1997, p. 104.
28. B. M. Kariuki, K. D. M. Harris, D. Philp and J. M. A. Robinson, J. Am. Chem. Soc., 1997, 119, 12 679.