Karczmarzyk Zbigniew, Lipińska Teodozja M, Wysocki Waldemar, Denisiuk Monika, Piechocka Katarzyna
Department of Chemistry, University of Podlasie, ul. 3 Maja 54, 08-110 Siedlce, Poland.
Acta Crystallogr C. 2011 Sep;67(Pt 9):o346-9. doi: 10.1107/S0108270111027272. Epub 2011 Aug 5.
In the crystal structures of the diastereoisomers of O-tosylcinchonidine [(9R)-cinchon-9-yl 4-methylbenzenesulfonate], (I), and O-tosylcinchonine [(9S)-cinchon-9-yl 4-methylbenzenesulfonate], (II), both C(26)H(28)N(2)O(3)S, both molecules are in an anti-closed conformation and, in each case, the position of the aryl ring of the tosylate system is influenced by an intramolecular C-H···O hydrogen bond. The molecular packing in (I) is influenced by weak intermolecular C-H···O and C-H···π interactions. The crystal structure of (II) features C-H···π interactions and van der Waals forces only. The computational investigations using RHF/6-31G** ab initio and AM1 semi-empirical methods performed for (I) and (II) and their protonated species show that the conformational and energetic parameters of the molecules are correlated with differences in their reactivity in hydrolysis to the corresponding 9-epibases.
在O-对甲苯磺酰辛可尼定[（9R）-辛可宁-9-基4-甲基苯磺酸盐]（I）和O-对甲苯磺酰辛可宁[（9S）-辛可宁-9-基4-甲基苯磺酸盐]（II）的非对映异构体的晶体结构中，二者化学式均为C(26)H(28)N(2)O(3)S，两个分子均处于反式封闭构象，并且在每种情况下，对甲苯磺酸盐体系的芳基环的位置受分子内C-H···O氢键影响。（I）中的分子堆积受弱分子间C-H···O和C-H···π相互作用影响。（II）的晶体结构仅具有C-H···π相互作用和范德华力。对（I）和（II）及其质子化物种使用RHF/6-31G**从头算和AM1半经验方法进行的计算研究表明，分子的构象和能量参数与它们水解生成相应9-表碱基的反应性差异相关。
