Molecular and crystal structure of 1,1 '-diamino-2,2 '-bipyridinium and 1,1 '-diamino-4,4 '-bipyridinium dimesitylenesulphonates: A combined experimental and theoretical study

Molecular and crystal structure of 1,1 '-diamino-2,2 '-bipyridinium and 1,1 '-diamino-4,4 '-bipyridinium dimesitylenesulphonates: A combined experimental and theoretical study Full article

Journal

Journal of Molecular Structure
ISSN: 0022-2860 , E-ISSN: 1872-8014

Output data

Year: 2013, Volume: 1035, Pages: 441-447 Pages count : 7 DOI: 10.1016/j.molstruc.2012.11.043

Tags

N,N '-diaminobipyridinium salts; Hydrogen bond; pi-Stacking; X-ray diffraction; DFT; MP2

Authors

Borodkin Gennady I. ^1,2 , Vorob'ev Alexey Yu. ^1,2 , Supranovich Vyacheslav I. ² , Gatilov Yury V. ¹ , Shubin Vyacheslav G. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia

The purpose of the present work is to study molecular and crystal structures of 1,1'-diamino-2,2'-bipyridinium (1a) and 1,1'-diamino-4,4'-bipyridinium (1b) dimesitylenesulphonates by experimental (X-ray, NMR) and theoretical (OFF, RI-B3LYP and RI-MP2) methods. The N-NH2 bond lengths determined by X-ray diffraction are close to that of single N-N bond and considerably longer than that of double N=N bond. The bipyridine fragment in dications is slightly asymmetric (sigma-pi distortion). The dihedral angle between the two pyridine planes in dication (1a) is essentially larger than that in dication (1b). The NH2 groups have a pyramidal structure. The crystal structure of 1,1'-diamino-2,2'-bipyridinium dimesitylensulphonate is a stack of layers of cations and anions. The basic supramolecular synthon is N-H center dot center dot center dot O. The directed along a + b axis zig-zag ribbons of cations in a crystal of 1,1'-diamino-4,4'-bipyridinium dimesitylenesulphonate are formed due to such a synthon and pseudo-para arrangement of amino groups. OFT and RI-MP2 calculations give geometry of the dications similar to the experimental one. The conformational analyses of dications (1a) and (1b) have been carried out using RI-B3LYP method. Non-planar conformation of dication (1a) in DMSO solution is confirmed by H-1 NMR data. Calculation of HOMA(d) index for the dications from the experimental bond lengths gives values which indicate their aromatic character. (c) 2012 Elsevier B.V. All rights reserved.

Borodkin G.I. , Vorob'ev A.Y. , Supranovich V.I. , Gatilov Y.V. , Shubin V.G.
Molecular and crystal structure of 1,1 '-diamino-2,2 '-bipyridinium and 1,1 '-diamino-4,4 '-bipyridinium dimesitylenesulphonates: A combined experimental and theoretical study
Journal of Molecular Structure. 2013. V.1035. P.441-447. DOI: 10.1016/j.molstruc.2012.11.043 WOS Scopus РИНЦ

Published print:

Mar 1, 2013

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