Comparison of N···I and N···O Halogen Bonds in Organoiodine Cocrystals of Heterocyclic Aromatic Diazine Mono- N -oxides
Comparison of N···I and N···O Halogen Bonds in Organoiodine Cocrystals of Heterocyclic Aromatic Diazine Mono- N -oxides
复制标题
杂环芳香族二嗪单氮氧化物有机碘共晶中 N····I 和 N···O 卤键的比较
DOI：
10.1021/acs.cgd.3c01344
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发表时间：
2024
影响因子：
3.8
通讯作者：
Guillet, Gary L.
中科院分区：
文献类型：
--
作者：
Padgett, Clifford W.;Dean, Riley;Cobb, Audrey;Miller, Aubree;Goetz, Andrew;Bailey, Sam;Hillis, Kyle;McMillen, Colin;Toney, Sydney;Guillet, Gary L.
研究了卤键给体1，4-二碘四氟苯（p-F4DIB）和四碘乙烯（TIE）与五种含吡嗪、四甲基吡嗪、喹喔啉、吩嗪和嘧啶的芳香杂环二嗪单N-氧化物的共晶。单-N-氧化物的结构分析允许比较N···I与O···I相互作用的竞争发生以及这两种类型相互作用的相对强度和方向性。在所研究的芳香杂环二嗪单-N-氧化物有机碘共晶体中，有6个呈现1：1的化学计量比，形成利用N···I和O···I相互作用的链。两种共晶呈现1：1的化学计量比，O···I相互作用不存在。两个共晶显示出2：1的化学计量比，一个仅由O···I相互作用表征，另一个仅由N···I相互作用表征。我们还比较了这些相互作用中存在的相应的二嗪，其中一些我们在这里报告，一些已被以前报道。此外，使用密度泛函理论（M062X/def2-SVPD）的计算分析，这两个系统进行，并已与实验结果进行了比较。计算的络合物形成能，平均，4.7 kJ/mol低的I···O卤素键相互作用相比，相应的N···I相互作用。计算出的平均I···O相互作用距离比相应的I···N相互作用距离短0.15 μ m。
A series of cocrystals of halogen bond donors 1,4-diiodotetrafluorobenzene (p-F4DIB) and tetraiodoethylene (TIE) with five aromatic heterocyclic diazine mono-N-oxides based on pyrazine, tetramethylpyrazine, quinoxaline, phenazine, and pyrimidine as halogen bonding acceptors were studied. Structural analysis of the mono-N-oxides allows comparison of the competitive occurrence of N···I vs O···I interactions and the relative strength and directionality of these two types of interactions. Of the aromatic heterocyclic diazine mono-N-oxide organoiodine cocrystals examined, six exhibited 1:1 stoichiometry, forming chains that utilized both N···I and O···I interactions. Two cocrystals presented 1:1 stoichiometry with exclusive O···I interactions. Two cocrystals displayed a 2:1 stoichiometry─one characterized solely by O···I interactions and the other solely by N···I interactions. We have also compared these interactions to those present in the corresponding diazines, some of which we report here and some which have been previously reported. In addition, a computational analysis using density functional theory (M062X/def2-SVPD) was performed on these two systems and has been compared to the experimental results. The calculated complex formation energies were, on average, 4.7 kJ/mol lower for the I···O halogen bonding interaction as compared to the corresponding N···I interaction. The average I···O interaction distances were calculated to be 0.15 Å shorter than the corresponding I···N interactions.