同构卤素交换和卤素键：N-（4-卤代苄基）-3-卤代吡啶鎓卤化物案例,Crystal Growth & Design

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同构卤素交换和卤素键：N-（4-卤代苄基）-3-卤代吡啶鎓卤化物案例
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2022-01-05 , DOI: 10.1021/acs.cgd.1c01285
Luka Fotović ₁ , Nikola Bedeković ₁ , Vladimir Stilinović ₁

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六种N- (4-卤代苄基)-3-卤代吡啶鎓阳离子通过间位反应制备-卤代吡啶（Cl、Br和I）与（4-卤代苄基）溴化物（Br和I）并以溴化物盐的形式分离，进一步用于获得碘化物和氯化物。获得了 16 种化合物（18 种可能的阳离子/阴离子组合）；两个结晶为水合物，14 个结晶为无溶剂盐，其中 11 个属于同构系列，3 个属于另一个同构系列。所有晶体结构都包含卤素键合链，阴离子作为两个卤素键的受体，两个相邻阳离子的吡啶和苄基卤素取代基。与吡啶卤素的卤素键显示出相对卤素键长和角度之间的线性相关性，这主要取决于供体卤素。其他卤素键的参数随所有三种卤素而变化，表明前一个卤素键是主要的相互作用。这也与卤素的 σ 空穴中计算的静电势和固体的热性质一致。第二个同构组包含最好的卤素键供体和受体的组合，并且具有更有利的卤素键的主要卤素键几何形状，重申其作为决定结构的主要因素的重要性。

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Isostructural Halogen Exchange and Halogen Bonds: The Case of N-(4-Halogenobenzyl)-3-halogenopyridinium Halogenides

Six N-(4-halogenobenzyl)-3-halogenopyridinium cations were prepared by reacting meta-halogenopyridines (Cl, Br, and I) with (4-halogenobenzyl) bromides (Br and I) and were isolated as bromide salts, which were further used to obtain iodides and chlorides. Sixteen compounds (out of 18 possible cation/anion combinations) were obtained; two crystallized as hydrates and 14 as solvent free salts, 11 of which belonged to one isostructural series and 3 to another. All crystal structures comprise halogen-bonded chains, with the anion as an acceptor of two halogen bonds, with the pyridine and the benzyl halogen substituents of two neighboring cations. The halogen bonds with the pyridine halogen show a linear correlation between the relative halogen bond length and angle, which primarily depend on the donor halogen. The parameters of the other halogen bonds vary with all three halogens, indicating that the former halogen bond is the dominant interaction. This is also in accord with the calculated electrostatic potential in the σ-holes of the halogens and the thermal properties of the solids. The second isostructural group comprises combinations of the best halogen bond donors and acceptors, and features a more favorable halogen bond geometry of the dominant halogen bond, reaffirming its significance as the main factor in determining the structure.

更新日期：2022-02-02

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