title: Polymorphism in beta-cyclodextrin-benzoic acid inclusion complex: a kinetically controlled crystal growth according to the Ostwald's rule.
abstract: Crystal form II of the beta-cyclodextrin-benzoic acid (beta-CD-BA) inclusion complex was obtained from the 1.5-year stored aqueous EtOH solution of beta-CD and BA as 2beta-CD.1.5BA.0.7EtOH.21H(2)O in the monoclinic space group C2 with unit cell constants: a=19.413(3), b=24.306(4), c=32.975(1)A, beta=104.41(1) degrees . By contrast, the desired crystal form I in the triclinic space group P1 that ever grew up from the fresh solution as 2beta-CD.2BA.0.7EtOH.20.65H(2)O was not reproducible any more [Aree, T.; Chaichit, N. Carbohydr. Res.2003, 338, 439-446]. In the two crystal forms, beta-CDs are isostructural with a 'round' conformation stabilized by intramolecular O-3(n)cdots, three dots, centeredO-2(n+1) hydrogen bonds. The BA inclusion geometries are similar with a preferred orientation, that is, BAs are situated above the O-4 plane, point their COOH groups to the beta-CD O-6 side, incline 52 degrees with respect to the O-4 plane and are mainly maintained in positions by hydrogen bonding with the surrounding water molecules. beta-CDs form dimers as structural motif of different packing modes: the screw-channel type in form II and the average of intermediate and tetrad types in form I. Polymorphism in the beta-CD-BA inclusion complex is a kinetically controlled crystal growth following the Ostwald's rule: the less stable crystal form I grew up first within one week from the fresh solution, whereas the more stable crystal form II appeared after 1.5-year storage.
authors.affiliation: Department of Chemistry, Faculty of Science, Chulalongkorn University, Phyathai Road, Pathumwan, Bangkok 10330, Thailand. thammarat.aree@gmail.com
authors.forename: Thammarat
authors.initials: T
authors.lastname: Aree
authors.forename: Narongsak
authors.initials: N
authors.lastname: Chaichit
authors.forename: Chainarong
authors.initials: C
authors.lastname: Engkakul
mesh_terms: D019817:Benzoic Acid / Q000737:chemistry*; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D003460:Crystallization; D006860:Hydrogen Bonding; D007700:Kinetics; D047028:Macrocyclic Compounds / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008969:Molecular Sequence Data; D047392:beta-Cyclodextrins / Q000737:chemistry*
chemical_list: D047028:Macrocyclic Compounds; D047392:beta-Cyclodextrins; D019817:Benzoic Acid; C031215:betadex