Cyanophenyloximes:: Reliable and versatile tools for hydrogen-bond directed supramolecular synthesis of cocrystals
Cyanophenyloximes:: Reliable and versatile tools for hydrogen-bond directed supramolecular synthesis of cocrystals
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DOI：
10.1021/cg0600492
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发表时间：
2006-04-01
影响因子：
3.8
通讯作者：
Desper, J
中科院分区：
文献类型：
--
作者：
Aakeröy, CB;Salmon, DJ;Desper, J
三种类型的苯肟R-C=N-OH（其中R = H，Me或CN）和一系列N-杂环氢键受体之间的共结晶反应所产生的产品的系统的结构和光谱检查表明，肟-OH氢键供体的酸性是至关重要的超分子组装过程的功效。氰基苯肟是可比的羧酸，在成功率方面，而显着较低的酸性CH 3-和H-取代的类似物是不是有效地产生共晶体，尽管空间和几何参数的密切相似性。使用实验pK（a）值和计算的静电势表面作为预测O-H中心点N相互作用驱动共晶形成的超分子产率的基础的重要性和有效性（在官能团类内）是明确建立的，提出了六种新的以肟中心点中心点杂环氢键组装的共晶结构。
A systematic structural and spectroscopic examination of the products resulting from cocrystallization reactions between three types of phenyloximes R-C=N-OH (where R = H, Me, or CN) and a series of N-heterocyclic hydrogen-bond acceptors demonstrates that the acidity of the oxime -OH hydrogen-bond donor is crucial to the efficacy of the supramolecular assembly process. Cyanophenyloximes are comparable to carboxylic acids, in terms of success rate, whereas the significantly less acidic CH3- and H-substituted analogues are not effective at generating cocrystals despite close similarities in steric and geometric parameters. The importance and validity of using experimental pK(a) values and calculated electrostatic potential surfaces as a basis for predicting the supramolecular yield of an O-H center dot center dot center dot N interaction for driving the formation of cocrystals (within a functional group class) is unambiguously established, and six new crystal structures of cocrystals assembled using oxime center dot center dot center dot heterocycle-based hydrogen bonds are presented.