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Volumn 8, Issue 9, 2008, Pages 3474-3481

Predictable disorder versus polymorphism in the rationalization of structural diversity: A multidisciplinary study of eniluracil

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EID: 56549097994     PISSN: 15287483     EISSN: 15287505     Source Type: Journal    
DOI: 10.1021/cg800517h     Document Type: Article
Times cited : (47)

References (62)
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    • Adherex Technologies Inc Eniluracil;
    • Adherex Technologies Inc Eniluracil; http://www.adherex.com/products/ eniluracil, 2007.
    • (2007)
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    • PXRD_1 (a) was determined from data recorded in transmission mode on the high-resolution powder X-ray diffractometer on Station 2.3 at the Synchrotron Radiation Source, Daresbury Laboratory. The powder X-ray diffraction pattern was indexed to give a monoclinic unit cell (a, 7.20 Å, b, 6.82 Å, c, 5.86 Å, β, 92.96°) and the space group was assigned from systematic absences as P21. Structure solution was carried out directly from the powder X-ray diffraction data using the direct-space genetic algorithm (GA) technique (b-d, incorporated in an early version of the program EAGER (e, The structure solution involved a single rigid molecule of eniluracil in the asymmetric unit. The best structure solution obtained in the GA calculation was taken as the starting structural model for Rietveld refinement using the program GSAS (f, final refined unit cell: a, 7.1969(8) Å, b, 6.8189(6) Å, c, 5.8633(7)
    • 1. Structure solution was carried out directly from the powder X-ray diffraction data using the direct-space genetic algorithm (GA) technique (b-d), incorporated in an early version of the program EAGER (e). The structure solution involved a single rigid molecule of eniluracil in the asymmetric unit. The best structure solution obtained in the GA calculation was taken as the starting structural model for Rietveld refinement using the program GSAS (f) (final refined unit cell: a = 7.1969(8) Å, b = 6.8189(6) Å, c = 5.8633(7) Å, β = 92.957(6)°). It was noted that there is selective broadening of some peaks in the powder X-ray diffraction pattern, which strongly alludes to the existence of stacking disorder of the sheets in the structure (the broadening is particularly prominent for the peak at 20 = 23.9°, which is indexed as (102) and corresponds to the planes of the sheets in the refined structure). No attempt was made to cany out Rietveld refinements for disordered structural models. (a) Psallidas, K.; Kariuki, B. M.; Harris, K. D. M.; Lancaster, R. W. Research Project Report Submitted to Glaxo Wellcome (23 April, 1999).
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    • Habershon, S, Zhou, Z, Turner, G. W, Kariuki, B. M, Cheung, E. Y, Hanson, A. J, Tedesco, E, Johnston, R. L, Harris, K. D. M. EAGER, A Computer Program for Direct-Space Structure Solution from Powder X-ray diffraction Data, Cardiff University and University of Birmingham
    • (e) Habershon, S.; Zhou, Z.; Turner, G. W.; Kariuki, B. M.; Cheung, E. Y.; Hanson, A. J.; Tedesco, E.; Johnston, R. L., Harris, K. D. M. EAGER - A Computer Program for Direct-Space Structure Solution from Powder X-ray diffraction Data, Cardiff University and University of Birmingham.
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    • Larson, A. C.; Von Dreele, R. B. GSAS, Los Alamos Laboratory Report No. LA-UR-86-748; Los Alamos National Laboratory: Los Alamos, NM, 1987.
    • (f) Larson, A. C.; Von Dreele, R. B. GSAS, Los Alamos Laboratory Report No. LA-UR-86-748; Los Alamos National Laboratory: Los Alamos, NM, 1987.
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    • 1/c, but the atomic coordinates of this structure are not available. Although the unit cell is very similar to that of structure 1, and we can reproduce the published packing diagrams using ak56 or one ordered component of 1, the difference in space group setting implies a different packing of the nonpolar ribbons. Our discussions with the authors show that it is now impossible to determine whether this is a genuine difference. Sacchetti, M.; Varlashkin, P. G.; Long, S. T.; Lancaster, R. W. J. Pharm. Sci. 2001, 90, 1049-1055.
    • 1/c, but the atomic coordinates of this structure are not available. Although the unit cell is very similar to that of structure 1, and we can reproduce the published packing diagrams using ak56 or one ordered component of 1, the difference in space group setting implies a different packing of the nonpolar ribbons. Our discussions with the authors show that it is now impossible to determine whether this is a genuine difference. Sacchetti, M.; Varlashkin, P. G.; Long, S. T.; Lancaster, R. W. J. Pharm. Sci. 2001, 90, 1049-1055.
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    • Since crystal structure determination from X-ray diffraction data gives an averaged representation of the actual structure over all unit cells in the crystal, we cannot deduce a priori whether the structure comprises: (a) ordered domains containing only orientation A and ordered domains containing only orientation B, or (b) a situation in which, in each region of the crystal, each individual molecule has a statistical probability of having orientation A or B. In case (b), the disorder exists at the molecular level and, in principle, the orientation of a given molecule may be uncorrelated with the orientations of its neighbours and can be dynamic or static. For case (a), the molecules in the ordered domains have a well-defined set of interactions with their neighbours (analogous to a conventional ordered crystal structure), whereas for case (b), a range of different local intermolecular environments may exist
    • Since crystal structure determination from X-ray diffraction data gives an averaged representation of the actual structure over all unit cells in the crystal, we cannot deduce a priori whether the structure comprises: (a) ordered domains containing only orientation A and ordered domains containing only orientation B, or (b) a situation in which, in each region of the crystal, each individual molecule has a statistical probability of having orientation A or B. In case (b), the disorder exists at the molecular level and, in principle, the orientation of a given molecule may be uncorrelated with the orientations of its neighbours and can be dynamic or static. For case (a), the molecules in the ordered domains have a well-defined set of interactions with their neighbours (analogous to a conventional ordered crystal structure), whereas for case (b), a range of different local intermolecular environments may exist, depending on the orientation of a given molecule and the set of orientations of its neighbors. Robinson, J. M. A.; Kariuki, B. M.; Harris, K. D. M.; Philp, D. J. Chem. Soc., Perkin Trans. 1998, 2, 2459.
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    • Violuric acid monohydrate does show this close C=O⋯O=C interaction of 2.779 Å in a symmetric ribbon structure, but this is stabilized by a water hydrogen bonding motif. Nichol, G. S.; Clegg, W. Acta Crystallogr., Sect. E 2005, 61, O3788-O3790.
    • Violuric acid monohydrate does show this close C=O⋯O=C interaction of 2.779 Å in a symmetric ribbon structure, but this is stabilized by a water hydrogen bonding motif. Nichol, G. S.; Clegg, W. Acta Crystallogr., Sect. E 2005, 61, O3788-O3790.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.