Molecular Conformation and Intermolecular Interactions in the Crystal Structures of Free-Base 5,15-Diarylporphyrins

Crystal Growth and Design

Volumn 2, Issue 1, 2002, Pages 27-39

  Bond, Andrew D ^a   Feeder, Neil ^a,c   Redman, James E ^a,d   Teat, Simon J ^b   Sanders, Jeremy K M ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

^b DARESBURY LABORATORY   (United Kingdom)

^c PFIZER GLOBAL RESEARCH AND DEVELOPMENT   (United Kingdom)

^d SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0013241153     PISSN: 15287483     EISSN: None     Source Type: Journal    
DOI: 10.1021/cg010029u     Document Type: Article

References (40)

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28. Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525-5534.
29. Use of the word "stack" is avoided here since it carries a very definite meaning in the context of the crystal structures of porphyrins. The interactions described are not typical offset π-stacking interactions, and so the motifs are described instead as "chains".
30. The molecular units are, of course, positioned across a crystallographic center of symmetry. Care should be taken, however, to avoid phrases such as "the molecule adopts an anti conformation, imposed by the crystallographic centre of symmetry"; this is quite incorrect. The anti conformation of the molecule arises because this conformation, coupled with the intermolecular interactions in the crystal, corresponds to a minimum in the free energy. The fact that the resulting conformation is centrosymmetric allows the crystal structure to be described as such, and not vice versa. The same applies for the observation that the phenyl substituents are exactly perpendicular to the porphyrin plane in the higher-symmetry molecular unit of 2α.
31. Balaban, T. S.; Eichhofer, A.; Lehn, J.-M. Eur. J. Org. Chem. 2000, 4047-4057.
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35. Sudhölter, E. J. R.; van Dijk, M.; Teunis, C. J.; Sanders, G. M.; Harkema, S.; van de Velde, G. M. H.; Schouten, P. G.; Warman, J. M. J. Mater. Chem. 1993, 6 (3), 357-363.
36. Darling, S.; Feeder, N.; Sanders, J. K. M. Private communication to the Cambridge Crystallographic Data Centre (CSD refcode: HOJBOX), 1999.
37. A note of caution is warranted when describing "primary" and other structural motifs - crystal structures reflect a balance of all intermolecular interactions, each with varying degrees of directionality and distance dependence. Control of this complex balance of forces in three dimensions is a formidable problem, and the crystal engineer must approach it by identifying predictable and robust supramolecular motifs. The discussion of "primary" motifs in this manner follows closely the "supramolecular synthon" approach of Desiraju (Desiraju, G. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 2311-2327).
38. This remark is clearly not applicable to metallo-porphyrins where introduction of the pyridyl substituents may facilitate coordination to axial metal sites of other porphyrins. A particularly relevant recent example is given by the crystal structure of the zinc complex of 9 (Wild, K. Y.; Therrien, B.; Plieger, P. G.; Officer, D. L.; Burrell, A. K. Acta Crystallogr. 2001, E57, m478-m479).
39. Nakash, M.; Clyde-Watson, Z.; Feeder, N.; Davies, J. E.; Teat, S. J.; Sanders, J. K. M. J. Am. Chem. Soc. 2000, 122, 5286-5293.
40. Senge, M. O.; Liddell, P. A.; Smith, K. M. Acta Crystallogr. 1992, C48, 581-583.