Crystal packing and melting temperatures of small oxalate esters: the role of C-H···O hydrogen bonding.

IF 1.9 3区 化学 Acta Crystallographica Section B-structural Science Pub Date : 2011-12-01 Epub Date: 2011-10-13 DOI:10.1107/S0108768111037487
Sumy Joseph, Ranganathan Sathishkumar, Sudarshan Mahapatra, Gautam R Desiraju
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引用次数: 13

Abstract

The simple dialkyl oxalates are generally liquids at room temperature except for dimethyl and di-tert-butyl oxalate which melt at 327 and 343 K. The crystal structures of diethyl, di-iso-propyl, di-n-butyl, di-tert-butyl and methyl ethyl oxalates were determined. The liquid esters were crystallized using the cryocrystallization technique. A comparison of the intermolecular interactions and packing features in these crystal structures was carried out. The crystal structure of dimethyl oxalate was redetermined at various temperatures. The other compounds were also studied at several temperatures in order to assess the attractive nature of the hydrogen bonds therein. A number of moderate to well defined C-H···O interactions account for the higher melting points of the two solid esters. Additionally, a diminished entropic contribution ΔS(m) in di-tert-butyl oxalate possibly increases the melting point of this compound further.

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小草酸酯的晶体堆积和熔化温度:C-H···O氢键的作用。
除二甲基和二叔丁基草酸盐在327 K和343 K熔化外,简单草酸二烷基在室温下一般为液体。测定了草酸二乙酯、二异丙基、二正丁基、二叔丁基和草酸甲酯的晶体结构。采用结晶技术对液体酯进行结晶。比较了这些晶体结构的分子间相互作用和堆积特性。在不同温度下重新测定了草酸二甲酯的晶体结构。其他化合物也在几个温度下进行了研究,以评估其中氢键的吸引力。大量的C-H··O相互作用是两种固体酯较高熔点的原因。此外,草酸二叔丁基的熵贡献ΔS(m)的减小可能进一步提高了该化合物的熔点。
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5.30%
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6-12 weeks
期刊介绍: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.
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