“Crystal-conformations of 2-methyl-2,4-pentanediol: Dipole moment calculations and molecular structure optimizations

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• 作者：O. V. Grineva (1)
  T. M. Usacheva (1)
  V. I. Zhuravlev (1)
  
• 关键词：Cambridge Structural Database ; quantum chemical calculations ; intra ; and intermolecular hydrogen bonds ; aliphatic diols
• 刊名：Journal of Structural Chemistry
• 出版年：2014
• 出版时间：January 2014
• 年：2014
• 卷：55
• 期：1
• 页码：161-168
• 全文大小：160 KB
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• 作者单位：O. V. Grineva (1)
  T. M. Usacheva (1)
  V. I. Zhuravlev (1)
  
  1. Moscow State University, Moscow, Russia
  
• ISSN：1573-8779

文摘

The structures of eight symmetrically independent molecules of 2-methyl-2,4-pentanediol (MPD) in six crystal substances are studied based on the data retrieved from the Cambridge Structural Database (CSD). Coordinates of the most part of hydrogen atoms in MPD molecules were not determined experimentally or not presented in CSD, however, O...O distances provide the conclusion about the formation of intramolecular hydrogen bonds in four molecules. To perform quantum chemical calculations the absent hydrogen atoms were added. The choice of H atomic positions in hydroxyl groups are based on the analysis of possible formation of intra- and intermolecular hydrogen bonds by MPD molecules in the respective crystals. The DFT method with the B3PW91 functional and the 6-31G(d,p) basis set is used to carry out for the first time: 1) the calculation of dipole moments and energies for MPD molecules in “crystal-conformations; 2) the optimization of the structure of these molecules with the calculation of dipole moments for the conformations corresponding to the local energy minima. It is found that among the molecules with the experimental geometric parameters one of the conformations without intramolecular hydrogen bonds is most favorable (μ = 0.56 D). As a result of the energy minimization of eight “crystal-conformations in vacuum, five energetically different conformers are obtained. Among them the conformer with the intramolecular hydrogen bond has the lowest energy (μ = 3.53 D). Four variants of the molecular structure correspond to it in the considered crystals, out of which two are R-enantiomers and two S-enantiomers.