Searching for a Polymorph: Second Crystal Form of 6‐Amino‐2‐Phenylsulfonylimino‐1,2‐Dihydropyridine
10.1002/anie.200250660
Crossref journal-article
Wiley
Angewandte Chemie International Edition (311)
Bibliography

Jetti, R. K. R., Boese, R., Sarma, J. A. R. P., Reddy, L. S., Vishweshwar, P., & Desiraju, G. R. (2003). Searching for a Polymorph: Second Crystal Form of 6‐Amino‐2‐Phenylsulfonylimino‐1,2‐Dihydropyridine. Angewandte Chemie International Edition, 42(17), 1963–1967. Portico.

Authors 6
  1. Ram K. R. Jetti (first)
  2. Roland Boese (additional)
  3. Jagarlapudi A. R. P. Sarma (additional)
  4. L. Sreenivas Reddy (additional)
  5. Peddy Vishweshwar (additional)
  6. Gautam R. Desiraju (additional)
References 33 Referenced 73
  1. 10.1038/nmat726
  2. 10.1107/S0108768102005669
  3. 10.1107/S0108768100004584
  4. 10.1021/cg015576u
  6. {'key': 'e_1_2_2_6_2', 'first-page': '471', 'volume-title': 'Organic Solid State Chemistry', 'author': 'Bernstein J.', 'year': '1987'} / Organic Solid State Chemistry by Bernstein J. (1987)
  7. {'key': 'e_1_2_2_7_2', 'first-page': '151', 'volume-title': 'Polymorphism in Molecular Crystals', 'author': 'Bernstein J.', 'year': '2002'} / Polymorphism in Molecular Crystals by Bernstein J. (2002)
  8. {'key': 'e_1_2_2_8_2', 'first-page': '325', 'volume-title': 'Crystal Engineering', 'author': 'Sarma J. A. R. P.', 'year': '1999'} / Crystal Engineering by Sarma J. A. R. P. (1999)
  9. {'key': 'e_1_2_2_9_2', 'first-page': '603', 'author': 'Hughes D. S.', 'year': '2001', 'journal-title': 'J. Chem. Soc. Chem. Commun.'} / J. Chem. Soc. Chem. Commun. by Hughes D. S. (2001)
  10. 10.1002/jps.2600740307
  11. {'key': 'e_1_2_2_11_2', 'first-page': '103', 'volume-title': 'Solid State Chemistry of Drugs', 'author': 'Byrn S. R.', 'year': '1982'} / Solid State Chemistry of Drugs by Byrn S. R. (1982)
  12. 10.1039/a706669d
  13. W. Schaap PhD thesis University of Essen (Germany) 2001.
  14. 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°.
  15. 10.1248/yakushi1881.59.3_213 / J. Pharm. Soc. Jpn. by Tuda K. (1939)
  16. This was carried out by flame‐sealing containers within which a saturated solution of1is present and then allowing them to stand for several days at room temperature.
  17. 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°.
  18. Crystal data for Form I (Nicolet R3 at room temperature): monoclinic P21/c a=8.5450(13) b=9.0638(17) c=15.151(2) Å β=91.492(12)° V=1173.0(3) Å3 Z=4 ρcalcd=1.412 g cm−3 T=293 K μ=0.269 mm−1 2θmax=60° 3526 measured 3403 independent 2687 observed (I>2σ1) reflections 154 parameters R1=0.0406 wR2=0.1072 (forI>2σ1) residual electron density +0.337/−0.296 e Å−3. Crystal data for Form I (SMART at 183 K): monoclinic P21/c a=8.479(5) b=8.958(5) c=14.894(8) Å β=91.856(10)° V=1130.7(11) Å3 Z=4 ρcalcd=1.464 g cm−3 T=183 K μ=0.279 mm−1 2θmax=56.18° 13 514 measured 2820 independent 2002 observed (I>2σ1) reflections 154 parameters R1=0.0495 wR2=0.1158 (forI>2σ1) residual electron density +0.597/−0.359 e Å−3. Crystal data for Form II: monoclinic P21/c a=12.1099(15) b=10.7924(12) c=17.464(2) Å β=97.318(2)° V=2263.9(5) Å3 Z=8 ρcalcd=1.463 g cm−3 T=203 K μ=0.279 mm−1 2θmax=56.6° 14 219 measured 5443 independent 2871 observed (I>2σ1) reflections 307 parameters R1=0.0579 wR2=0.1200 (for I>2σ1) residual electron density +0.496/−0.339 e Å−3. The data were collected on a Nicolet R3 or on a SMART diffractometer using MoKαradiation. Structure solution was by direct methods and refinements onF2with SHELXTL (Version 6.10 and 6.12). Non‐hydrogen atoms were refined anisotropically and the H atoms of the phenyl groups were generated at idealised geometries and refined isotropically using a riding model. The H atom positions of the NH2and 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 CB2 1EZ UK; fax: (+44) 1223‐336‐033; or deposit@ccdc.cam.ac.uk).
  19. 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.
  20. These observations suggest that CSP protocols for a “right” answer should definitely take into account such structural variations.
  21. 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]).
  22. 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.
  23. Energy calculations were carried out using the CVFF95 force field in the Cerius2program. Cerius2 Accelrys Cambridge (UK). See www.accelrys.com.
  24. {'key': 'e_1_2_2_24_2', 'first-page': '1', 'volume': '4', 'author': 'Beyer T.', 'year': '2001', 'journal-title': 'CrystEngComm'} / CrystEngComm by Beyer T. (2001)
  25. 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‐ray‐observed geometry with normalized H atom distances.
  26. The lattice‐energy calculations were carried out in the two forms with H‐normalized molecules. The Crystal Packer module which is part of the Cerius2program environment was used. Similar potentials as defined earlier were used. No minimization of either cell parameters or molecular positions was carried out.
  27. SynthonAis 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 synthonB.
  28. 10.1002/(SICI)1096-987X(199803)19:4<459::AID-JCC6>3.0.CO;2-R
  29. The fact that Form II is the thermodynamic form is also corroborated by the method of obtaining crystals from increasingly dilute solutions.
  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:
  31. {'key': 'e_1_2_2_31_2', 'volume-title': 'Grundriss der Allgemeinen Chemie,', 'author': 'Ostwald W.', 'year': '1899'} / Grundriss der Allgemeinen Chemie, by Ostwald W. (1899)
  32. 10.1021/ja9626345
  33. 10.1021/ar00052a005
Dates
Type When
Created 22 years, 4 months ago (April 30, 2003, 11:01 a.m.)
Deposited 1 year, 10 months ago (Oct. 11, 2023, 12:24 p.m.)
Indexed 1 year ago (July 31, 2024, 6:29 a.m.)
Issued 22 years, 4 months ago (April 29, 2003)
Published 22 years, 4 months ago (April 29, 2003)
Published Online 22 years, 4 months ago (April 30, 2003)
Published Print 22 years, 4 months ago (April 29, 2003)
Funders 0

None

@article{Jetti_2003, title={Searching for a Polymorph: Second Crystal Form of 6‐Amino‐2‐Phenylsulfonylimino‐1,2‐Dihydropyridine}, volume={42}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.200250660}, DOI={10.1002/anie.200250660}, number={17}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Jetti, Ram K. R. and Boese, Roland and Sarma, Jagarlapudi A. R. P. and Reddy, L. Sreenivas and Vishweshwar, Peddy and Desiraju, Gautam R.}, year={2003}, month=apr, pages={1963–1967} }