A Systematic Experimental and Theoretical Study of the Crystalline State of Six Chloronitrobenzenes

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• 作者：Sarah A. Barnett ; Andrea Johnston ; Alastair J. Florence ; Sarah L. Price ; Derek A. Tocher
• 刊名：Crystal Growth & Design
• 出版年：2008
• 出版时间：January 2008
• 年：2008
• 卷：8
• 期：1
• 页码：24 - 36
• 全文大小：3505K
• 年卷期：v.8,no.1(January 2008)
• ISSN：1528-7505

文摘

Experimental and computational searches for the crystal structures of the five commercially available isomers of dichloronitrobenzene and 3,4-dinitrochlorobenzene were performed to assess the relationship between functional group interactions and steric requirements in determining the solid forms. Experimentally, this resulted in the first crystal structure determination of 2,4-dichloronitrobenzene, two solvates of 3,4-dichloronitrobenzene and one of 3,4-dinitrochlorobenzene. Additionally, low temperature redeterminations of the crystal structures were obtained for 2,5-dichloronitrobenzene, 3,4-dichloronitrobenzene, and both the β- and γ-forms of 3,4-dinitrochlorobenzene. The searches for energetically feasible structures of each of these compounds showed a wide variety of distributions leading to varying degrees of clarity of prediction of the solid state behavior. These range from 2,3-dichloronitrobenzene, which only adopts the crystal structure that was clearly the most thermodynamically stable of all five isomers, through complex systems, which show a range of low energy minima indicating possible polymorphism and solvate formation, to 2,4-dichloronitrobenzene, which can conformationally distort and adopts a complicated Z′ = 2 crystal structure.