The relationship between the crystal habit and the energy framework pattern: a case study involving halogen bonding on the edge of a covalent bond
The relationship between the crystal habit and the energy framework pattern: a case study involving halogen bonding on the edge of a covalent bond
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晶体习性与能量框架模式之间的关系：共价键边缘卤素键合的案例研究
DOI：
10.1039/d3ce00316g
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发表时间：
2023
期刊：
影响因子：
3.1
通讯作者：
Rosokha, Sergiy V.
中科院分区：
文献类型：
--
作者：
Torubaev, Yury V.;Howe, Devin;Leitus, Gregory;Rosokha, Sergiy V.
固态超分子相互作用和晶体习性之间的关系是突出的基础上的强卤素键合（HaB）的含碘二卤素（ICl，IBr）与1，4-二氮杂双环[2，2，2]辛烷（DABCO）以及取代的吡啶和吩嗪之间的关联的晶体结构的实验和计算分析。的能量框架的图案和相互作用的吸引力和排斥力的相互作用在固态协会涉及这些HaB的捐助者和受体直接与他们的晶体习性。这种相关性表明，分析的能量框架作为一个有用的工具（补充早期开发的方法），合理化和预测的晶体习性。X射线结构分析还显示，复合物中的I N距离在2.24-2.54 Å范围内，即它们更接近I N共价键长度，而不是货车范德华力间距。计算分析表明，这些配合物中卤素键的性质是由于给体和受体之间的分子轨道离域，导致大量的电荷从亲核试剂转移到二卤原子上，从而导致I-X键的伸长。因此，在最强的络合物中I N和I X都成键（例如，ICl与DABCO或4-二甲基氨基吡啶）的特征在于可比较的约0.6的Mayer键级，沿着在它们的键临界点处的电子和能量密度为约0.1 a.u.和-0.02 a.u.，分别这些数据以及密度重叠区域指示器（DORI）指向I N键合的共价性，并表明IX络合物内的相互作用可以描述为（不对称）超价3c/4 e N I X键合，类似于三卤离子或卤离子中的键合。
The relationship between solid-state supramolecular interactions and crystal habits is highlighted based on experimental and computational analysis of the crystal structure of strong halogen-bonded (HaB) associations between iodine-containing dihalogens (ICl, IBr) with 1,4-diazabicyclo[2,2,2]octane (DABCO) as well as with substituted pyridines and phenazine. The pattern of the energy frameworks and the interplay of the attractive and repulsive interactions in the solid-state associations involving these HaB donors and acceptors directly correlated with their crystal habits. This correlation suggests that analysis of the energy framework serves as a useful tool (complementary to the earlier developed methods) to rationalize and predict the crystal habit. The X-ray structural analysis also revealed that the I⋯N distances in the complexes were in the 2.24–2.54 Å range, i.e. they were much closer to the I⋯N covalent bond length than to the van der Waals separation. The computational analysis of the nature of halogen bonding in these complexes showed delocalization of their molecular orbitals' between donor and acceptors resulting in a substantial charge transfer from the nucleophiles to dihalogens and elongation of the I⋯X bond. As a result, both I⋯N and I⋯X bonds in the strongest complexes (e.g., ICl with DABCO or 4-dimethylaminopyridine) are characterized by the comparable Mayer bonds orders of about 0.6, along with the electron and energy densities at their bond critical points of about 0.1 a.u. and −0.02 a.u., respectively. These data as well as the density overlap regions indicator (DORI) point to the covalency of the I⋯N bonding and suggest that the interaction within the IX complexes can be described as (unsymmetrical) hypervalent 3c/4e N⋯I⋯X bonding akin to that in trihalide or halonium ions.