eprintid: 1472682
rev_number: 24
eprint_status: archive
userid: 608
dir: disk0/01/47/26/82
datestamp: 2015-11-18 14:01:16
lastmod: 2021-09-19 23:59:33
status_changed: 2015-11-18 14:01:16
type: article
metadata_visibility: show
creators_name: Hylton, RK
creators_name: Tizzard, GJ
creators_name: Threlfall, TL
creators_name: Ellis, AL
creators_name: Coles, SJ
creators_name: Seaton, CC
creators_name: Schulze, E
creators_name: Lorenz, H
creators_name: Seidel-Morgenstern, A
creators_name: Stein, M
creators_name: Price, SL
title: Are the crystal structures of enantiopure and racemic mandelic acids determined by kinetics or thermodynamics?
ispublished: pub
divisions: UCL
divisions: B04
divisions: C06
divisions: F56
note: This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
abstract: Mandelic acids are prototypic chiral molecules where the sensitivity of crystallized forms (enantiopure/racemic compound/polymorphs) to both conditions and substituents provides a new insight into the factors that may allow chiral separation by crystallization. The determination of a significant number of single crystal structures allows the analysis of 13 enantiopure and 30 racemic crystal structures of 21 (F/Cl/Br/CH3/CH3O) substituted mandelic acid derivatives. There are some common phenyl packing motifs between some groups of racemic and enantiopure structures, although they show very different hydrogen-bonding motifs. The computed crystal energy landscape of 3-chloromandelic acid, which has at least two enantiopure and three racemic crystal polymorphs, reveals that there are many more possible structures, some of which are predicted to be thermodynamically more favorable as well as slightly denser than the known forms. Simulations of mandelic acid dimers in isolation, water, and toluene do not differentiate between racemic and enantiopure dimers and also suggest that the phenyl ring interactions play a major role in the crystallization mechanism. The observed crystallization behavior of mandelic acids does not correspond to any simple "crystal engineering rules" as there is a range of thermodynamically feasible structures with no distinction between the enantiopure and racemic forms. Nucleation and crystallization appear to be determined by the kinetics of crystal growth with a statistical bias, but the diversity of the mandelic acid crystallization behavior demonstrates that the factors that influence the kinetics of crystal nucleation and growth are not yet adequately understood.
date: 2015-09-02
date_type: published
official_url: http://dx.doi.org/10.1021/jacs.5b05938
oa_status: green
full_text_type: pub
primo: open
primo_central: open_green
article_type_text: Journal Article
verified: verified_manual
elements_id: 1047818
doi: 10.1021/jacs.5b05938
language_elements: eng
lyricists_name: Price, Sarah
lyricists_id: SLPRI40
actors_name: Price, Sarah
actors_name: Poirier, Elizabeth
actors_id: SLPRI40
actors_id: EPPOI23
actors_role: owner
actors_role: impersonator
full_text_status: public
publication: Journal of the American Chemical Society
volume: 137
number: 34
pagerange: 11095-11104
event_location: United States
issn: 1520-5126
citation:        Hylton, RK;    Tizzard, GJ;    Threlfall, TL;    Ellis, AL;    Coles, SJ;    Seaton, CC;    Schulze, E;                 ... Price, SL; + view all <#>        Hylton, RK;  Tizzard, GJ;  Threlfall, TL;  Ellis, AL;  Coles, SJ;  Seaton, CC;  Schulze, E;  Lorenz, H;  Seidel-Morgenstern, A;  Stein, M;  Price, SL;   - view fewer <#>    (2015)    Are the crystal structures of enantiopure and racemic mandelic acids determined by kinetics or thermodynamics?                   Journal of the American Chemical Society , 137  (34)   pp. 11095-11104.    10.1021/jacs.5b05938 <https://doi.org/10.1021/jacs.5b05938>.       Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/1472682/1/jacs.5b05938.pdf