Molecular-dynamics simulation of crystalline 18-crown-6: thermal shortening of covalent bonds

Abstract

Molecular-dynamics simulations of crystalline 18crown-6 have been performed in a study of the apparent thermal shortening of covalent bonds observed in crystal structures. At 100 K, a shortening of 0.006 _+ 0.001 A for C----C and C----O bonds was obtained. This result was found to be independent of details of the force field and the simulation. There was agreement between computational and experimental values for the thermal parameters, as well as for the molecular geometry (bond and dihedral angles) of 18-crown-6. Some differences are attributed to the inability of the force field to reproduce hydrogen-bonding geometries. Simulation at 295 K resulted in an estimated shortening of 0.019_+ 0.005 A. Thus at room temperature for C--C bonds (apparent) thermal shortening and (real) chemical shortening, resulting from the electronegative oxygen * I UPAC name: 1,4,7,10,13,16-hexaoxacyclooctadecane. 0108-7681/90/020222-08503.00 substituents, are of the same order of magnitude. In the simulation at 295 K occasional dihedral transitions were observed, which may reflect the proximity of the melting point (312 K). derived from diffraction experiments The shortening of the C--C bonds to values in the range 1-46-1.52 A has been called the 'macrocyclic C--C shortening effect' The same effect is found, however, in linear polyethers (Weber, Hirayama, Saenger &