Structural analysis of cyclodextrins: A comparative study of classical and quantummechanical methods

In the present work, we analyzed the accuracy of distinct theoretical methods to reproduce the solid state structures of cyclodextrins. The alpha, beta and gamma-cyclodextrins (CD) were considered and also their hydrates with included water molecules: alpha-CD.2H(2)O, beta-CD.10H(2)O and gamma-CD.12H(2)O. The geometries were fully optimized using Molecular Mechanics (MM2), semiempirical (AM1 and PM3) and ab initio (HF/3-21G) methods and quantitatively compared with experimental data from X ray diffraction. The results obtained from the classical MM2 method were in best agreement with the experiment. The semiempirical and ab initio structures were also in satisfactory accordance with the experimental data. In general, the PM3 method was found to be more suitable than the AM1 to describe the CD geometries, mainly when the intramolecular hydrogen bonds are considered.