Search for a predicted hydrogen bonding motif : a multidisciplinary investigation into the polymorphism of 3-Azabicyclo[3.3.1]nonane-2,4-dione
Hulme, Ashley T. and Johnston, Andrea and Florence, Alastair J. and Fernandes, Phillipe and Shankland, Kenneth and Bedford, Colin T. and Welch, Gareth W. A. and Sadiq, Ghazala and Haynes, Delia A. and Motherwell, W. D. Samuel and Tocher, Derek A. and Price, Sarah L. (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, 129 (12). pp. 3649-3657. ISSN 1520-5126 (https://doi.org/10.1021/ja0687466)
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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.
ORCID iDs
Hulme, Ashley T., Johnston, Andrea, Florence, Alastair J. ORCID: https://orcid.org/0000-0002-9706-8364, Fernandes, Phillipe, Shankland, Kenneth, Bedford, Colin T., Welch, Gareth W. A., Sadiq, Ghazala, Haynes, Delia A., Motherwell, W. D. Samuel, Tocher, Derek A. and Price, Sarah L.;-
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Item type: Article ID code: 10987 Dates: DateEvent1 March 2007Published6 December 2006AcceptedSubjects: Medicine > Pharmacy and materia medica Department: Faculty of Science > Strathclyde Institute of Pharmacy and Biomedical Sciences Depositing user: Strathprints Administrator Date deposited: 02 Dec 2011 12:11 Last modified: 19 Sep 2024 12:46 URI: https://strathprints.strath.ac.uk/id/eprint/10987