Chiral and achiral crystals, charge-assisted hydrogen-bond patterns and self-organization of selected solid diaminium thiosulfates

Agnieszka Brozdowska; Jarosław Chojnacki

doi:10.1107/s2052520617004802

Chiral and achiral crystals, charge-assisted hydrogen-bond patterns and self-organization of selected solid diaminium thiosulfates

Abstract

Abstract A series of diaminium thiosulfates, derivatives of diamines: NH2CH2CH(CH3)NH2 (1) and NH2(CH2)nNH2, n = 3-6 (2-5 respectively)and thiosulfuric acid were prepared and their structures determined by crystal X-ray diffraction analysis. Compounds 1, 2 and 4 turned out to be hydrates. The crystal structure of 1,2-proylenediaminium thiosulfate is chiral and exhibits spontaneous resolution. Crystals for both enantiomers (1a and 1b) were obtained and examined. An extended network of strong, charge-assisted hydrogen bonding of the (+)N–H∙∙∙O(-) type (also O–H∙∙∙O and O–H∙∙∙S for hydrates) is most likely the main factor defining crystal packing and variable conformation of the cations. Formation of non-centrosymmetric hydrogen bond motifs – distorted cubans – seems to induce the formation of chiral solid state structure from achiral components in the case of 4. Diaminiumthiosulaftes with an odd number of carbon atoms in alkyl chain (compounds 1, 2, 4) form 3D supramolecular networks, while in the case of diaminium salts with an even number of carbon atoms (3 and 5), 2D layers of hydrogen bond domains are observed. The aminium thiosulfates were also characterized by elemental analysis, NMR, and FTIR spectroscopy. Conformations of α,ω-alkyldiaminiumcations in the solid state are discussed and rationalized by DFT calculations.

Citations

2

CrossRef
0

Web of Science
2

Scopus

Authors (2)

Cite as

Full text

download paper

downloaded 52 times

Publication version: Accepted or Published Version
License: Copyright (International Union of Crystallography)

Keywords

Details

Category:

Articles

Type:

artykuł w czasopiśmie wyróżnionym w JCR

Published in:

Acta Crystallographica Section B-Structural Science Crystal Engineering and Materials no. 73, edition 3, pages 507 - 518,
ISSN: 2052-5206

Language:

English

Publication year:

2017

Bibliographic description:

Brozdowska A., Chojnacki J.: Chiral and achiral crystals, charge-assisted hydrogen-bond patterns and self-organization of selected solid diaminium thiosulfates// Acta Crystallographica Section B-Structural Science Crystal Engineering and Materials. -Vol. 73, iss. 3 (2017), s.507-518

DOI: