2-Pyridylselenenyl versus 2-Pyridyltellurenyl Halides: Symmetrical Chalcogen Bonding in the Solid State and Reactivity towards Nitriles

Ivan V Buslov,Victor N Khrustalev,Tatiyana V Serebryanskaya,Andreii S Kritchenkov,Alexey S Kubasov,Mariya V Grudova,Alexander S Novikov,Anatoly A Kirichuk,Maria M Grishina,Julia M Lukiyanova,Alexander G Tskhovrebov,Zhanna V Matsulevich,Alexander V Borisov

doi:10.3390/sym13122350

Abstract

The synthesis of 2-pyridyltellurenyl bromide via Br2 oxidative cleavage of the Te–Te bond of dipyridylditelluride is reported. Single-crystal X-ray diffraction analysis of 2-pyridyltellurenyl bromide demonstrated that the Te atom of 2-pyridyltellurenyl bromide was involved in four different noncovalent contacts: Te⋯Te interactions, two Te⋯Br ChB, and one Te⋯N ChB contact forming 3D supramolecular symmetrical framework. In contrast to 2-pyridylselenenyl halides, the Te congener does not react with nitriles furnishing cyclization products. 2-Pyridylselenenyl chloride was demonstrated to easily form the corresponding adduct with benzonitrile. The cyclization product was studied by the single-crystal X-ray diffraction analysis, which revealed that in contrast to earlier studied cationic 1,2,4-selenadiazoles, here we observed that the adduct with benzonitrile formed supramolecular dimers via Se⋯Se interactions in the solid state, which were never observed before for 1,2,4-selenadiazoles.

Highlights

2-pyridylselenenyl chloride readily forms compare its self-assembly in the solid-state with structurally similar selenium co an adduct with PhCN, the Te analog does not react with benzonitrile or any other simple
In an extension of our earlier works, here we demonstrate that benzonitrile reacts with 1 forming cationic 1,2,4-selenadiazole 15 in excellent yield (Scheme 1)
Inspection of the crystallographic data revealed the presence of several nontrivial noncovalent interactions in the crystal structures 1, 15, and 16

Summary

Introduction

In contrast to halogen bonding (XB) or hydrogen bonding (HB), usage of ChB in crystal engineering, preparative chemistry, sensing, etc., is still emerging [10]. ChB allows modulation of the self-assembly and, fine-tuning their utilization in the preparation of soft materials with tunable physicalofparamet charge transport within these heterocycles. Compare its within self-assembly the solid-state with structurally similar selenium congener, 2pyridylselenenyl chloride, and the reactivity of these two 2-pyridylchalcogenenyl. 2-pyridylselenenyl chloride readily forms compare its self-assembly in the solid-state with structurally similar selenium co an adduct with PhCN, the Te analog does not react with benzonitrile or any other simple. 2-pyridylselenenyl chloride, and compare the reactivity of these two 2-pyridy nitrile tested in the framework of the current study. Specified, chemicals were purchased from the commercial sources. NMR data was obtained on a Bruker Avance neo 700; chemical shifts are given in ppm, coupling constants in Hz

Materials and Methods

Clsolvent

Discussion

Ball-and-stick

Laplacians of electron density distribution