Mixed Crystals in Chiral Organic Systems: A Case Study on (R)- and (S)‑Ethanolammonium 3‑Chloromandelate N. V. Taratin,* ,† H. Lorenz, ‡ E. N. Kotelnikova, † A. E. Glikin, †,¶ A. Galland, § V. Dupray, § G. Coquerel, § and A. Seidel-Morgenstern ‡ † Saint-Petersburg State University, Crystallography Dept., St. Petersburg, 199034, Russia ‡ Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, 39106, Germany § Rouen University, SMS Laboratory, UPRES EA 3233, IRCOF, Mont-Saint-Aignan Cedex, 76821, France * S Supporting Information ABSTRACT: This work focuses on characterization of chiral organic systems with partial solid solutions. Particularly, behavior of the (R)- and (S)-ethanolammonium 3-chloromandelates (E3ClMA) has been investigated experimentally. Partial solid solutions of the series (R)-E3ClMA−(Rac)-E3ClMA and (S)-E3ClMA−(Rac)- E3ClMA were discovered at the eutectic type of the binary phase diagram by means of systematic differential scanning calorimetry and X-ray powder diffraction measurements. Solubility and metastable zone width were measured for solutions of (R)-E3ClMA, (Rac)-E3ClMA, and their mixtures in ethanol as the solvent. The crystal structure of the pure (R)-E3ClMA was successfully determined by single- crystal X-ray diffraction. Several efforts of single crystals productions from (R, S) solutions were made by means of cooling and evaporation methods. Crystal morphology changes from well-shaped crystals for the pure enantiomer to spherulites for the racemic composition. 1. INTRODUCTION Mixed crystals (solid solutions, isomorphic mixtures) occur quite often in organic and inorganic systems as well as they present a majority of natural minerals. Understanding of mixed crystal formation processes has become an object of special scientific interest in different fields due to a feasible creation of smart materials with predetermined properties and elaboration of new approaches to mineral genesis reconstructions. Crystal chemistry and thermodynamics of solid solutions were successfully developed during the 20th century, especially for inorganic substances in frames of metallurgy and mineralogy. 1,2 Some concepts for organic mixed crystals were also elaborated. 1,3−5 During the last 30 years, 6 the genetic concept was established for mixed crystals. 7 However, a comprehensive theory of mixed crystal formation, which could be applied for a priori design of mixed crystal properties, is not elaborated yet. A pair of enantiomers represents molecules of mirror antipodes. The molecules have identical physical properties (apart from opposite optical rotation) but cause different effects on biological systems. Therefore, the enantiomeric purity of a material plays an essential role in the pharmaceutical and food industry. An equimolar mixture of two antipodes produces an optically inactive solution. The substance crystallized from such a solution is called a racemate. Composition ranges of “(R)- enantiomer−racemic composition” and “(S)-enantiomer−race- mic composition” are equal due to the mirror symmetry of the corresponding phase diagrams. 8 The type of phase diagram is related to the nature of a racemate. A mechanical mixture of enantiomers refers to a racemic conglomerate and corresponds to a eutectic system. Structural ordering of enantiomers inside a crystal corresponds to a racemic compound and occurs in a congruent melting system. Continuous solid solutions in chiral organic systems are a rare case (∼1%). Furthermore, partial solid solutions of enantiomers in eutectic and congruent melting systems occur much more often than expected in the past; some examples were described in the literature recently. 9−12 This work focuses on verification and characterization of partial solid solutions of the (S)- and (R)-enantiomers of the ethanolamine salt of 3-chloromandelic acid (E3ClMA, Figure 1). This research originates from a comparison between E3ClMA with the ethanolammonium mandelate, which forms Received: March 12, 2012 Revised: October 23, 2012 Published: October 24, 2012 Figure 1. Ethanolamine salt of 3-chloromandelic (E3ClMA). Position of the chiral center is marked by the dot. Article pubs.acs.org/crystal © 2012 American Chemical Society 5882 dx.doi.org/10.1021/cg3003405 | Cryst. Growth Des. 2012, 12, 5882−5888