Structural systematics and conformational analyses of a 3 × 3 isomer grid of fluoro-N-(pyridyl)benzamides: physicochemical correlations, polymorphism and isomorphous relationships.

IF 1.9 3区 化学 Acta Crystallographica Section B-structural Science Pub Date : 2012-04-01 Epub Date: 2012-03-20 DOI:10.1107/S0108768112006799
Pavle Mocilac, Katie Donnelly, John F Gallagher
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引用次数: 31

Abstract

An isomer grid of nine fluoro-N-(pyridyl)benzamides (Fxx) (x = para-/meta-/ortho-) has been examined to correlate structural relationships between the experimental crystal structure and ab initio calculations, based on the effect of fluorine (Fx) and pyridine N-atom (x) substitution patterns on molecular conformation. Eight isomers form N-H⋅⋅⋅N hydrogen bonds, and only one (Fom) aggregates via intermolecular N-H⋅⋅⋅O=C interactions exclusively. The Fpm and Fom isomers both crystallize as two polymorphs with Fpm_O (N-H⋅⋅⋅O=C chains, P-syn) and Fpm_N (N-H⋅⋅⋅N chains, P-anti) both in P2(1)/n (Z' = 1) differing by their meta-N atom locations (P-syn, P-anti; N(pyridine) referenced to N-H), whereas the disordered Fom_O is mostly P-syn (Z' = 6) compared with Fom_F (P-anti) (Z' = 1). In the Fxo triad twisted dimers form cyclic R(2)(2)(8) rings via N-H⋅⋅⋅N interactions. Computational modelling and conformational preferences of the isomer grid demonstrate that the solid-state conformations generally conform with the most stable calculated conformations except for the Fxm triad, while calculations of the Fox triad predict the intramolecular N-H⋅⋅⋅F interaction established by spectroscopic and crystallographic data. Comparisons of Fxx with related isomer grids reveal a high degree of similarity in solid-state aggregation and physicochemical properties, while correlation of the melting point behaviour indicates the significance of the substituent position on melting point behaviour rather than the nature of the substituent.

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氟- n -(吡啶基)苯酰胺3 × 3异构体网格的结构系统和构象分析:物理化学相关性、多态性和同构关系。
基于氟(Fx)和吡啶n原子(x)取代模式对分子构象的影响,研究了九种氟- n -(吡啶基)苯酰胺(Fxx) (x =对-/间-/邻位-)的异构体网格,以将实验晶体结构与从头计算之间的结构关系联系起来。8个异构体形成N- h⋅⋅N氢键,只有1个异构体(form)完全通过分子间N- h⋅⋅O=C相互作用聚集。Fpm和form异构体都结晶为两种多晶型,Fpm_O (N- h⋅⋅O=C链,P-syn)和Fpm_N (N- h⋅⋅N链,P-anti)都在P2(1)/ N (Z' = 1)中,不同的是它们的元N原子位置(P-syn, P-anti;N(pyridine)参考N- h),而无序的Fom_O主要是P-syn (Z' = 6),而Fom_F (P-anti) (Z' = 1)。在Fxo中,三联体扭曲二聚体通过N- h⋅⋅N相互作用形成环状R(2)(2)(8)环。异构体网格的计算模型和构象偏好表明,固态构象一般符合除Fxm三元组外最稳定的计算构象,而Fox三元组的计算预测了通过光谱和晶体学数据建立的分子内N-H⋅⋅⋅F相互作用。Fxx与相关异构体栅格的比较揭示了固态聚集和物理化学性质的高度相似性,而熔点行为的相关性表明取代基位置对熔点行为的重要性,而不是取代基的性质。
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来源期刊
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5.30%
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0
审稿时长
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.
期刊最新文献
The charge-flipping algorithm in crystallography. The role of the coordination defect (CD) in the structures of anion-deficient, fluorite-related compounds. Structural transformations in the low-temperature grown GaAs with superlattices of Sb and P δ-layers. Electronic influence of β-diketonato-type ligands on the coordination of 1,5-cyclooctadiene to palladium(II) as defined by 'Venus fly trap' geometric parameters. Weak intermolecular hydrogen and halogen interactions in an isomorphous halogen series of pseudoterpyridine Zn(II) complexes.
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