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Volumn 107, Issue 48, 2003, Pages 13523-13531

Lamellar racemic twinning as an obstacle for the resolution of enantiomers by crystallization: The case of Me(All)N+(CH2Ph)Ph X- (X = Br, I) salts

Author keywords

[No Author keywords available]

Indexed keywords

CALCULATIONS; COMPOSITION; CRYSTAL GROWTH; CRYSTALLIZATION; MASS SPECTROMETRY; MOLECULAR STRUCTURE; NITROGEN; POSITIVE IONS; SALTS; SINGLE CRYSTALS; TWINNING; X RAY DIFFRACTION ANALYSIS;

EID: 0348207685     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp035588l     Document Type: Article
Times cited : (36)

References (75)
  • 9
  • 25
    • 84991190195 scopus 로고
    • This phenomenon was found to happen for other crystal symmetries as well: (a) Heller, E.; Schmidt, G. M. J. Isr. J. Chem. 1971, 9, 449.
    • (1971) Isr. J. Chem. , vol.9 , pp. 449
    • Heller, E.1    Schmidt, G.M.J.2
  • 28
    • 0346115375 scopus 로고    scopus 로고
    • note
    • -3 % (w/w)), and the planes do not translate themselves. Thus, the X-ray reflections for twinned crystals and pure enantiomeric crystals differ only by an anomalous correction.
  • 35
    • 0004547596 scopus 로고
    • Zur Stereochemie des Fünfwertigen Stickstoffes: Mit Besonderer Berucksightigung des Asymmetrischen Stickstoffes in der Aromatischen Reihe
    • Verlag von Veit & Co.: Leipzig, Germany
    • Wedekind, E. Zur Stereochemie des Fünfwertigen Stickstoffes: Mit Besonderer Berucksightigung des Asymmetrischen Stickstoffes in der Aromatischen Reihe; Verlag von Veit & Co.: Leipzig, Germany, 1899.
    • (1899)
    • Wedekind, E.1
  • 38
    • 0004547596 scopus 로고
    • Zur Stereochemie des Fünfwertigen Stickstoffes: Mit Besonderer Berucksightigung des Asymmetrischen Stickstoffes in der Aromatischen Reihe
    • Verlag von Veit & Co.: Leipzig, Germany
    • (c) Wedekind, E. Zur Stereochemie des Fünfwertigen Stickstoffes: Mit Besonderer Berucksightigung des Asymmetrischen Stickstoffes in der Aromatischen Reihe; Verlag von Veit & Co.: Leipzig, Germany, 1899; pp 31-53.
    • (1899) , pp. 31-53
    • Wedekind, E.1
  • 41
    • 0348006686 scopus 로고    scopus 로고
    • note
    • In the case of conglomerate, the solubility of the racemic mixture is approximately double that of the pure enantiomer (in an ideal case, the solubility of one enantiomer is not modified by the presence of the other); therefore, the crystals of the superfluous enantiomer first have to appear from solution enriched by this enantiomer.
  • 48
    • 0004575036 scopus 로고
    • note
    • It is without a doubt that W. J. Pope clearly realized the nature of Pasteur's experiments, and he and his colleague F. S. Kipping made a significant contribution to the further understanding of the spontaneous resolution phenomenon. We refer readers to two references: (a) Kipping, F. S.; Pope, W. J. J. Chem. Soc., Trans. 1898, 73, 606.
    • (1898) J. Chem. Soc., Trans. , vol.73 , pp. 606
    • Kipping, F.S.1    Pope, W.J.2
  • 49
    • 0038626009 scopus 로고
    • note
    • (b) Kipping, F. S.; Pope, W. J. J. Chem. Soc., Trans. 1897, 71, 989. The first one is dedicated to an elegant investigation of the crystallization of sodium chlorate. The second one is about their interpretation of the pseudoracemism phenomenon, where there is confirmation that the authors had an idea about twinning between enantiomers; however, they used this concept for the structural description of pseudoracemates, which is not actually correct.
    • (1897) J. Chem. Soc., Trans. , vol.71 , pp. 989
    • Kipping, F.S.1    Pope, W.J.2
  • 50
    • 0346115374 scopus 로고    scopus 로고
    • note
    • In ref 7j, the authors proposed the use of the term lamellar epitaxy instead of the term lamellar twinning for the description of cases of twinning of opposite enantiomers of the same chemical compound. They bases this idea on the definition of J. D. Dunitz (Acta Crystallogr., Sect. B 1995, 51, 619) that enantiomeric crystals of a conglomerate and a racemate are three different chemical substances if the enantiomerization rate is low and can be considered to be polymorphs if the enantiomerization rate is high. It is seems that the authors solved the confusion because even the same enantiomer can form lamellar twinned crystals, whereas the crystal growth of one substance on crystals of the other it is accepted as epitaxy. However, the confusion arises again if we take into consideration the fact that under certain conditions the enantiomerization rate can be high (for example, the presence of a catalyst or high temperature, which can increase the enantiomerization rate), whereas under another set of conditions the rate will be low. Therefore, in the first case the term twinning is appropriate, but in the second we should use the term epitaxy. We are inclined to take another point of view. Racemate-conglomerate polymorphism takes place when crystallization occurs from solution or in a melt of racemic composition and molecules or ions can assemble equiprobably into racemic crystals (racemic compound) or mechanical mixture of left- and right-handed crystals (conglomerate). To distinguish the ordinary twinning of crystals of the same enantiomer from the twinning of alternating lamellae of two opposite enantiomers leading to crystals of racemic composition, we suggest that the term lamellar racemic twinning be used. We refer readers also to ref 13a, where the term twinning by inversion for twinning between the two opposite enantiomers is proposed.
  • 68
    • 0034695348 scopus 로고    scopus 로고
    • The references for works dealing with salt ion clusters are in Zhang, D.; Cooks, R. G. Int. J. Mass Spectrom. 2000, 195/196, 667.
    • (2000) Int. J. Mass Spectrom. , vol.195-196 , pp. 667
    • Zhang, D.1    Cooks, R.G.2
  • 69
    • 0346745945 scopus 로고    scopus 로고
    • note
    • Although ESI MS is widely used for the investigation of self-assembly processes in solution, we think that this technique is of limited use for crystal nucleation studies. Other types of equipment such as cold-spray MS (ref 36) or sonic-spray MS (ref 37) are more promising.
  • 70
    • 0346115372 scopus 로고    scopus 로고
    • note
    • +, etc.), which are usually added for the purpose of charging neutral molecules and that actually serve as artificial promoters for clusterization.


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