Noncovalent Sulfoxide–Nitrile Coupling Involving Four-Center Heteroleptic Dipole–Dipole Interactions between the Sulfinyl and Nitrile Groups,Crystal Growth & Design

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Noncovalent Sulfoxide–Nitrile Coupling Involving Four-Center Heteroleptic Dipole–Dipole Interactions between the Sulfinyl and Nitrile Groups
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-04-09 , DOI: 10.1021/acs.cgd.0c00196
Daniil M. Ivanov ₁ , Sergey V. Baykov ₁ , Alexander S. Novikov ₁ , Galina Romanenko ₂ , Nadezhda A. Bokach ₁ , Robert A. Evarestov ₁ , Vadim Yu. Kukushkin _{1,

3}

Affiliation

The 4-X-5-nitro substituted phthalodinitriles (X = Br 1, I 2) were crystallized from Me₂SO solutions affording crystalline adducts (1–2)·Me₂SO, which were characterized by X-ray crystallography at various temperatures (>40 K). The two adducts are isomorphic and exhibit in their XRD structures the heteroleptic dipole–dipole four-center contacts between the S=O and C≡N functionalities. Results of DFT calculations within the “molecular” approach based on the experimental X-ray geometries of (1–2)·Me₂SO followed by the topological analysis of the electron density distribution (QTAIM analysis) at the M06-2X/x2c-TZVPPall level of theory confirm the presence of sulfoxide–nitrile heteroleptic dipole–dipole interactions in the solid state (their estimated strength does not exceed 7 kcal/mol). DFT calculations for 1·Me₂SO were also performed in both the periodic and “molecular” models at the DFT M06 level of theory using DZVP and pob-TZVP bases; the results of the electron density topological analysis are similar in both models.

中文翻译：

亚砜基和腈基团之间涉及四中心杂合子偶极-偶极相互作用的非共价亚砜-腈偶联

4 X-5硝基取代的phthalodinitriles（X = Br的1，我2）购自我结晶_2种SO溶液，得到结晶的加合物（1 - 2 ·Me）的₂ SO，将其特征在于在不同温度下的X射线晶体学（> 40 K）。这两个加合物是同构的，并且在它们的XRD结构中表现出S = O和C≡N官能团之间的杂配偶极-偶极四中心接触。基于（1 – 2）·Me ₂的实验X射线几何结构，“分子”方法内DFT计算的结果SO继之以M06-2X / x2c-TZVPPall理论水平的电子密度分布的拓扑分析（QTAIM分析）证实了固态存在亚砜-腈杂合偶极-偶极相互作用（其估计强度不超过7 kcal / mol）。在DFT M06的理论水平上，还使用DZVP和pob-TZVP碱，在周期性和“分子”模型中对1 ·Me ₂ SO进行了DFT计算。在两个模型中，电子密度拓扑分析的结果相似。

更新日期：2020-04-09

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