The melting point alternation in α,ω-alkanediols and α,ω- alkanediamines: Interplay between hydrogen bonding and hydrophobic interactions

Angewandte Chemie - International Edition

Volumn 39, Issue 5, 2000, Pages 918-922

  Thalladi, Venkat R ^a   Boese, Roland ^a   Weiss, Hans Christoph ^a  

^a UNIVERSITY OF DUISBURG ESSEN   (Germany)

Author keywords

Alkanes; Hydrogen bonds; Hydrophobic interactions; Melting point alternation; Structure property relationships

Indexed keywords

ALKANE DERIVATIVE; ALKANEDIOL DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; GEOMETRY; HYDROGEN BOND; HYDROPHOBICITY; MELTING POINT; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS;

EID: 0034599007     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000303)39:5<918::AID-ANIE918>3.0.CO;2-E     Document Type: Article

References (37)

1. G. A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures, Springer, Berlin, 1991.
2. a) T. E. Creighton, Proteins: Structures and Molecular Principles, Freeman, New York, 1987;
3. b) A. M. Davis, S. J. Teague, Angew. Chem. 1999, 111, 778; Angew. Chem. Int. Ed. 1999, 38, 736;
4. b) A. M. Davis, S. J. Teague, Angew. Chem. 1999, 111, 778; Angew. Chem. Int. Ed. 1999, 38, 736;
5. c) C. Tanford, The Hydrophobic Effect: Formation of Micelles and Biological Membranes, Wiley, New York, 1973;
6. d) A. Ullman, Chem. Rev. 1996, 96, 1533;
7. e) R. S. Clegg, J. E. Hutchison, J. Am. Chem. Soc. 1999, 121, 5319;
8. f) J.-M. Lehn, Supramolecular Chemistry: Concepts and Perspectives, VCH, Weinheim, 1995:
9. g) J. Wang, F. Leveiller, D. Jacquemain, K. Kjaer, J. Als-Nielsen, M. Lahav, L. Leiserowitz, J. Am. Chem. Soc. 1994, 116, 1192;
10. h) Y. Xia, G. M. Whitesides. Angew. Chem. 1998. 110, 568; Angew. Chem. Int. Ed. 1998, 37, 550.
11. h) Y. Xia, G. M. Whitesides. Angew. Chem. 1998. 110, 568; Angew. Chem. Int. Ed. 1998, 37, 550.
12. G. R. Desiraju, Angew. Chem. 1995, 107, 2541; Angew. Chem. Int. Ed. Engl. 1995, 34, 2311.
13. G. R. Desiraju, Angew. Chem. 1995, 107, 2541; Angew. Chem. Int. Ed. Engl. 1995, 34, 2311.
14. A. I. Kitaigorodskii, Molecular Crystals and Molecules, Academic Press, New York, 1973.
15. F. L. Breusch, Fortschr. Chem. Forsch. 1969, 12, 119.
16. R. Boese, H. C. Weiss, D. Bläser, Angew. Chem. 1999. 111, 1042; Angew. Chem. Int. Ed. 1999, 38, 988.
17. R. Boese, H. C. Weiss, D. Bläser, Angew. Chem. 1999. 111, 1042; Angew. Chem. Int. Ed. 1999, 38, 988.
18. a) R. Boese, M. Nussbaumer in Organic Crystal Chemistry, Vol. 7 (Eds.: D. W. Jones, A. Katrusiak), Oxford University Press, Oxford, 1994, pp. 20-37;
19. b) V. R. Thalladi, H. C. Weiss, D. Bläser, R. Boese, A. Nangia, G. R. Desiraju, J. Am. Chem. Soc. 1998, 120, 8702;
20. c) For further details, see: http://www. ohed-system.com.
21. 3 (CCDC-132875). Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-132862 to CCDC-132874.
22. The crystal structures of some of the compounds studied here have been reported. The analyses were carried out at different temperatures and sometimes to lower accuracies: a) 1,2-ethanediol at 130 K: R. Boesc, H. C. Weiss, Acta Crystallogr. Sect. C 1998, 54, 24;
23. b) 1,6-hexanediol at 300 K: M. Lindgren, T. Gustafsson, J. Westerling, A. Lund, Chem. Phys. 1986, 106, 441;
24. c) 1,9-nonanediol and 1,10-decanediol at 100 K: ref. [2g]:
25. d) 1,2-ethanediamine at 210 K: S. Jamet-Deleroix. Acta Crystallogr. Sect. B 1973, 29, 977;
26. e) 1,6-hexanediamine at 300 K: W. P. Binnie, J. M. Robertson, Acta Crystallogr. 1950, 3, 424;
27. f) 1,7-heplanediamine at 210 K: R. Gotthardt, J. H. Fuhrhop, J. Buschmann, P. Luger, Acta Crystallogr. Sect. C 1997. 53, 17105.
28. C. P. Brock, L. L. Duncan, Chem. Mater. 1994, 6, 1307.
29. V. K. Thalladi, H.-C. Weiss, R. Boese, A. Nangia, G. R. Desiraju, Acta Crystallogr. Sect. B 1999, 55, 1005, and references therein.
30. The geometries of the O-H ⋯ O bonds are similar at the two ends of the molecules, which also holds for C4 and C6-diols where Z′ = 1.
31. This is further corroborated by the fact that the calculated packing fractions for even diols and even diamines are systematically higher than those for the corresponding odd members (Table 1) and exhibit an alternating trend similar to that of the melting points and densities.
32. 2 program. All calculations were performed as the snapshots of crystal structures. The overall result is the same even after the crystal structures were minimized.
33. One of the C-O groups adopts a strained gauche conformation in odd diols in the solid state, which also contributes to the lowering of the melting points of odd diols.
34. Increased hydrophobicity does not alter the structural patterns in diols. Higher analogues of even and odd diols (a) 1,11-undecanediol: N. Nakamura, S. Setodoi, T. Ikeya, Acta. Crystallogr. Sect. C 1999, 55, 789;
35. b) 1,12-dodecanediol: N. Nakamura, S. Setodoi, Acta. Crystallogr. Sect. C 1997, 53, 1883;
36. c) 1,13-tridecanediol: N. Nakamura, Y. Tanihara, T. Takayama, Acta. Crystallogr. Sect. C 1997, 53, 253;
37. d) 1,16-hexadecanediol: N. Nakamura, T. Yamamoto, Acta. Crystallogr. Sect. C 1994, 50, 946) adopt structures isomorphous to their lower analogues.