Molecular recognition at the solid-solution interface: a relay mechanism for the effect of solvent on crystal growth and dissolution

Understanding and control of nucleation, growth, habit, dissolution and structure of two- and three-dimensional crystals using `tailor-made' auxiliaries

“…On the {011} faces, only two of the four symmetry-related molecules can be substituted by methanol and so inhibition of {011} should be less dramatic. This reasoning proved to be in keeping with experiment (Shimon, Vaida, Addadi, Lahav & Leiserowitz, 1991); growth in the presence of methanol as additive yielded {010} plates similar in shape to when asparagine is grown in the presence of aspartic acid [ Fig. 15(b)].…”

“…It was found that solvent may act in a manner similar to the tailor-made additives, for example, by growing (la) from acetic acid (Shimon, Vaida, Addadi, Lahav & Leiserowitz, 1991) instead of methanol. Acetic acid is a solvent which can selectively bind at the exposed carboxylic acid groups of the two {1 [ 1] faces, forming a hydrogen-bonded dimer (2a).…”

“…Such crystals were grown in the added presence of tailor-made solvent, which is a slightly modified version of the solvate solvent. It was found when crystalline hydrates were grown from aqueous solution in the added presence of methanol (the 'tailor-made' solvent), that the change in morphology was interpretable (Shimon, Vaida, Addadi, Lahav & Leiserowitz, 1990, 1991 in a manner akin to the effect of a tailor-made inhibitor. This approach is illustrated with the crystal of a-rhamnose monohydrate, which contains a polar arrangement [ Fig.…”

“…With occlusion of the additive into the crystal, the symmetry of the crystal may be reduced, thus making a 'centrosymmetric' crystal emit a second harmonic signal on irradiation with a laser beam (Weissbuch, Lahav, Leiserowitz, Meredith & Vanherzeele, 1989). Molecular crystals can be etched at desired faces on dissolution (Shimon, Lahav & Leiserowitz, 1985 and the effect of solvent on crystal growth may be elucidated (Wireko et al, 1987;Shimon, Vaida, Addadi, Lahav & Leiserowitz, 1990, 1991. Crystallization of a desired phase may be induced for the resolution of chiral molecules (Addadi, van Mil & Lahav, 1982;Addadi, Weinstein, Gati, Weissbuch & Lahav, 1982), or for the precipitation of a polar crystal polymorph (Staab, Addadi, Leiserowitz & Lahav, 1990).…”

Crystal structure of 1-[bis(p-toluenesulfonyl)amino]-2-(p-toluenesulfonylamino)-3-nitrobenzene, C27H25N3O8S3

“…Classical hydrogen bonding has played an important role in crystal engineering and has been investigated in much detail [1,2], while the studies of other weak interactions, such as the C-H×××O hydrogen bonds and the C-H×××p interactions have received attention only in more recentyears.The abilityofthe C-Hgroupsto actasdonorsinthe hydrogen bondswas amatter of debate and controversy in the past [3].Inrecent years, it is increasingly recognized that C-H×××Ohydrogen bonds play an important role in determining molecular conformation and crystal packing [4],in molecular recognition processes [5],inthe stabilization of inclusion complexes [6], and possibly in the activity of biological macromolecules [7]. The C-H×××p interactions represent another structural motif that is also commonly encountered in supramolecular and bioorganic chemistry [8,9].…”