Hydrogen bound self-associates N-(6-bromocyclohex-3-уn-1-yl)- and N-(7-bromobicyclo[2.2.1]hept-2-yl)-N′-(triflyl)ethanimidamide

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Abstract

The supramolecular structure of N -(6-bromocyclohex-3-en-1-yl)- and N -(7-bromobicyclo[2.2.1]hept-2-yl) N ′-(triflyl)ethanimidamide was analyzed according to XRD and IR spectroscopy in various states in a wide temperature range and quantum chemical calculations. The supramolecular structure of the studied amidines is based on linear dimers of the E-syn -conformer with N-H∙∙∙O=S hydrogen bonds, which form polymer chains. The layered structure of N -(6-bromocyclohex-3-en-1-yl)- N ′-(triflyl)ethanimidamide is formed by C-H∙∙∙O, C-H∙∙∙Br, and C-H∙∙∙F contacts, and in the case of N -(7-bromobicyclo[2.2.1]hept-2-yl)- N ′-(triflyl)ethanimidamide by C-H∙∙∙O contacts. The molecular electrostatic potential maps of the studied amidines were obtained and their correspondence between the strengths of H-bonds and shortened contacts in both compounds was shown. Comparison of experimental and calculated frequencies ν(NH) in monomers and dimers of N -(6bromocyclohex-3-en-1-yl)- N ′-(triflyl)ethanimidamide showed the presence of conformational E-syn → E-anti transitions with the formation of cyclic dimers, the proportion of which increases with decreasing temperature.

About the authors

L. P Oznobikhina

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

N. N Chipanina

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

I. V Sterkhova

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

V. V Astakhova

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

M. Yu. Moskalik

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

B. A Shainyan

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

Email: bagrat@irioch.irk.ru

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