Search for a predicted hydrogen bonding motif: a multidisciplinary investigation into the polymorphism of 3-Azabicyclo[3.3.1]nonane-2,4-dione

A.T. Hulme, A. Johnston, A.J. Florence, P. Fernandes, K. Shankland, C.T. Bedford, G.W.A. Welch, G. Sadiq, D.A. Haynes, W.D.S. Motherwell, D.A. Tocher, S.L. Price

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

The predictions of the crystal structure of 3-azabicyclo[3.3.1]nonane-2,4-dione submitted in the 2001 international blind test of crystal structure prediction (CSP2001) led to the conclusion that crystal structures containing an alternative hydrogen bonded dimer motif were energetically competitive with the known catemer-based structure. Here we report an extensive search for a dimer-based crystal structure. Using an automated polymorph screen a new catemer-based metastable polymorph (form 2) and two new catemer-based solvates were found, and concurrent thermal studies reproduced form 2 and identified a plastic phase (form 3), whose powder X-ray diffraction pattern was consistent with the cubic space group I23 (a = 7.5856(1) Å). Computational studies on the monomer showed that the imide N−H was a weak hydrogen bond donor, rationalizing the occurrence of the plastic phase which involved the breaking of all hydrogen bonds, and modeling of small clusters showed that dimers could easily reorganize to give the catemer. FTIR spectra confirmed the weakness of the hydrogen bond, with the solute showing no self-assembly in solution. It is concluded that the weakness of the N−H donor, coupled with the globular shape of the molecule, allows unusually facile transformation between alternative hydrogen bonding motifs during aggregation and nucleation.
LanguageEnglish
Pages3649-3657
Number of pages9
JournalJournal of American Chemical Society
Volume129
Issue number12
DOIs
Publication statusPublished - 2007

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Hydrogen Bonding
Polymorphism
Hydrogen
Hydrogen bonds
Crystal structure
Dimers
Plastics
Imides
Fourier Transform Infrared Spectroscopy
X-Ray Diffraction
Powders
Self assembly
Diffraction patterns
Cohort Studies
Nucleation
Agglomeration
Hot Temperature
Monomers
X rays
Molecules

Keywords

  • hydrogen bonding motif

Cite this

Hulme, A.T. ; Johnston, A. ; Florence, A.J. ; Fernandes, P. ; Shankland, K. ; Bedford, C.T. ; Welch, G.W.A. ; Sadiq, G. ; Haynes, D.A. ; Motherwell, W.D.S. ; Tocher, D.A. ; Price, S.L. / Search for a predicted hydrogen bonding motif : a multidisciplinary investigation into the polymorphism of 3-Azabicyclo[3.3.1]nonane-2,4-dione. In: Journal of American Chemical Society. 2007 ; Vol. 129, No. 12. pp. 3649-3657.
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Hulme, AT, Johnston, A, Florence, AJ, Fernandes, P, Shankland, K, Bedford, CT, Welch, GWA, Sadiq, G, Haynes, DA, Motherwell, WDS, Tocher, DA & Price, SL 2007, 'Search for a predicted hydrogen bonding motif: a multidisciplinary investigation into the polymorphism of 3-Azabicyclo[3.3.1]nonane-2,4-dione' Journal of American Chemical Society, vol. 129, no. 12, pp. 3649-3657. https://doi.org/10.1021/ja0687466

Search for a predicted hydrogen bonding motif : a multidisciplinary investigation into the polymorphism of 3-Azabicyclo[3.3.1]nonane-2,4-dione. / Hulme, A.T.; Johnston, A.; Florence, A.J.; Fernandes, P.; Shankland, K.; Bedford, C.T.; Welch, G.W.A.; Sadiq, G.; Haynes, D.A.; Motherwell, W.D.S.; Tocher, D.A.; Price, S.L.

In: Journal of American Chemical Society, Vol. 129, No. 12, 2007, p. 3649-3657.

Research output: Contribution to journalArticle

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AU - Hulme, A.T.

AU - Johnston, A.

AU - Florence, A.J.

AU - Fernandes, P.

AU - Shankland, K.

AU - Bedford, C.T.

AU - Welch, G.W.A.

AU - Sadiq, G.

AU - Haynes, D.A.

AU - Motherwell, W.D.S.

AU - Tocher, D.A.

AU - Price, S.L.

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AB - The predictions of the crystal structure of 3-azabicyclo[3.3.1]nonane-2,4-dione submitted in the 2001 international blind test of crystal structure prediction (CSP2001) led to the conclusion that crystal structures containing an alternative hydrogen bonded dimer motif were energetically competitive with the known catemer-based structure. Here we report an extensive search for a dimer-based crystal structure. Using an automated polymorph screen a new catemer-based metastable polymorph (form 2) and two new catemer-based solvates were found, and concurrent thermal studies reproduced form 2 and identified a plastic phase (form 3), whose powder X-ray diffraction pattern was consistent with the cubic space group I23 (a = 7.5856(1) Å). Computational studies on the monomer showed that the imide N−H was a weak hydrogen bond donor, rationalizing the occurrence of the plastic phase which involved the breaking of all hydrogen bonds, and modeling of small clusters showed that dimers could easily reorganize to give the catemer. FTIR spectra confirmed the weakness of the hydrogen bond, with the solute showing no self-assembly in solution. It is concluded that the weakness of the N−H donor, coupled with the globular shape of the molecule, allows unusually facile transformation between alternative hydrogen bonding motifs during aggregation and nucleation.

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