Searching for a polymorph: Second crystal form of 6-amino-2-phenylsulfonylimino-1,2-dihydropyridine

Angewandte Chemie - International Edition

Volumn 42, Issue 17, 2003, Pages 1963-1967

  Jetti, Ram K R ^b   Boese, Roland ^b   Sarma, Jagarlapudi A R P ^c   Reddy, L Sreenivas ^a   Vishweshwar, Peddy ^a   Desiraju, Gautam R ^a  

^a UNIVERSITY OF HYDERABAD   (India)

^b UNIVERSITY OF DUISBURG ESSEN   (Germany)

^c GVK BIOSCIENCES PVT LTD   (India)

Author keywords

Crystal growth; Hydrogen bonding; Polymorphism; Structure elucidation; Supramolecular chemistry

Indexed keywords

CHEMICAL BONDS; CRYSTAL STRUCTURE; HYDROGEN BONDS; LATTICE CONSTANTS; THERMODYNAMICS;

LATTICE ENERGIES;

AROMATIC COMPOUNDS;

6 AMINO 2 PHENYLSULFONYLIMINO 1,2 DIHYDROPYRIDINE; PYRIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CRYSTAL STRUCTURE; ENERGY; HYDROGEN BOND; KINETICS; MOLECULAR BIOLOGY; SUPRAMOLECULAR CHEMISTRY; THERMODYNAMICS;

EID: 0037878049     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200250660     Document Type: Article

References (31)

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4. J. A. R. P. Sarma, G. R. Desiraju, Cryst. Growth Des. 2002, 2, 93-100.
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7. "Polymorphism and Pseudopolymorphism in Organic Crystals: A Cambridge Structural Database Study":J. A. R. P. Sarma, G. R. Desiraju in Crystal Engineering (Eds.: K. R. Seddon, M. Zaworotko), Kluwer, Norwell, MA, 1999, pp. 325-356.
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12. W. Schaap, PhD thesis, University of Essen (Germany), 2001.
13. The C-C-S-N torsion angle is 26.0°. Only two other comparable structures in the CSD have such low torsion angles. They are (N(4-aminophenyl)sulfonyl)guanidine (ZZZAYP03; -12.5°) and 2-methyl-1-(2-methylphenyl)-3-(p-tosyl)-isothiourea (UCISOO; 24.9°). A total of 315 other comparable fragments have torsion angles between 60 and 90°.
14. The title compound was prepared according to the literature procedure for 2-(aminobenzenesulfonylamino)-6-aminopyridine (K. Tuda, Z. Izikawa, D. So, J. Pharm. Soc. Jpn. 1939, 59, 213-215). The compound was purified by column chromatography and recrystallized from MeOH.
15. This was carried out by flame-sealing containers within which a saturated solution of 1 is present, and then allowing them to stand for several days at room temperature.
16. M. Hursthouse, private communication, 2001; the reported cell parameters are: a = 8.251, b = 8.964, c = 15.087 Å, α = 90, β = 91.21, γ = 90°.
17. 2 and NH groups were taken from a difference Fourier map and were refined isotropically. CCDC 195422-195424 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
18. The differences between some of the unit-cell parameters in the two experiments are significantly greater than the changes brought about by lowering the temperature to 183 K. Accordingly, this fact is brought to the reader's attention.
19. These observations suggest that CSP protocols for a "right" answer should definitely take into account such structural variations.
20. The role of solvent in determining the polymorphic form obtained has been widely appreciated, but systematic efforts at understanding this phenomenon are scarce. In particular, the behavior of nitromethane in disrupting certain hydrogen-bonded aggregates in sulfathiazole crystallization has been described (see ref. [10]).
21. Note that we are specifying a torsion angle about what is formally a C=N bond. A comparison of the two symmetry-independent molecules in Form II suggests that there is considerable flexibility in this region of the molecule.
22. 2, Accelrys, Cambridge (UK). See www.accelrys.com.
23. T. Beyer, T. Lewis, S. L. Price, CrystEngComm 2001, 4, 1-35.
24. Clusters of three molecules that are connected by N-H⋯O and N-H⋯N interactions were used to calculate the relative energies in each case using the CVFF95 force field with explicit inclusion of both intra- and intermolecular interactions. The geometries of the three molecules in each case correspond to the X-rayobserved geometry with normalized H atom distances.
25. 2 program environment, was used. Similar potentials, as defined earlier, were used. No minimization of either cell parameters or molecular positions was carried out.
26. Synthon A is not strictly zero-dimensional (like the carboxylic acid dimer) because it has extra sites for N-H⋯O hydrogen bonding. But it is undoubtedly of lower dimensionality than synthon B.
27. [4] see also: W. T. M. Mooji, B. P. van Eijck, S. L. Price, P. Verwer, J. Kroon, J. Comput. Chem. 1998, 19, 459-474.
28. The fact that Form II is the thermodynamic form is also corroborated by the method of obtaining crystals from increasingly dilute solutions.
29. This is another demonstration of Ostwald's Law of Stages, which has been shown to be of wide applicability in studies of crystallization and polymorphism. See: a) W. Ostwald, Grundriss der Allgemeinen Chemie, Leipzig, 1899; b) R. J. Davey, N. Blagden, G. D. Potts, R. Doherty, J. Am. Chem. Soc. 1997, 119, 1767-1772.
30. This is another demonstration of Ostwald's Law of Stages, which has been shown to be of wide applicability in studies of crystallization and polymorphism. See: a) W. Ostwald, Grundriss der Allgemeinen Chemie, Leipzig, 1899; b) R. J. Davey, N. Blagden, G. D. Potts, R. Doherty, J. Am. Chem. Soc. 1997, 119, 1767-1772.
31. J. D. Dunitz, J. Bernstein, Acc. Chem. Res. 1995, 28, 193-200.