University of Oulu

Vasantha Gowda, Bipul Sarma, Risto S. Laitinen, Anna-Carin Larsson, Alexander V. Ivanov, Dinu Iuga, Perttu Lantto, Oleg N. Antzutkin, Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (13C/15N) CP-MAS NMR and DFT calculations, Polyhedron, Volume 129, 17 June 2017, Pages 123-132, ISSN 0277-5387, (

Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (¹³C/¹⁵N) CP-MAS NMR and DFT calculations

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Author: Gowda, Vasantha1,2; Sarma, Bipul3; Laitinen, Risto S.4;
Organizations: 1Chemistry of Interfaces, Luleå University of Technology, SE-97187 Luleå, Sweden
2NMR Research Unit, University of Oulu, P.O. Box 3000, FI-90014 Oulu, Finland
3Department of Chemical Sciences, Tezpur University, 784028 Tezpur, Assam, India
4Laboratory of Inorganic Chemistry, University of Oulu, P.O. Box 3000, FI-90014, Finland
5Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences, Blagoveshchensk 675000, Russia
6Department of Physics, Warwick University, Coventry CV4 7AL, UK
Format: article
Version: accepted version
Access: embargoed
Persistent link:
Language: English
Published: Elsevier, 2017
Publish Date: 2019-06-17


Two crystalline polymorphs of a binuclear tris(di-n-butyldithiocarbamato)bismuth(III) complex, I and II, with an empirical formula of [Bi{S2CN(n-C4H9)2}3] were synthesised and characterised by X-ray diffraction (XRD), solid-state NMR and density functional theory (DFT) calculations. At the supramolecular level, these mononuclear molecular units interact in pairs via secondary Bi⋯S bonds, yielding binuclear formations of [Bi2{S2CN(n-C4H9)2}6]. The polymorph I (P1) contains two isomeric non-centrosymmetric binuclear molecules of [Bi2{S2CN(n-C4H9)2}6], which are related to each other as conformers, therefore having four structurally inequivalent bismuth atoms and twelve inequivalent dithiocarbamate ligands. In contrast, the structurally simpler polymorph II (P21/n) exists as a single molecular form of the corresponding centrosymmetric binuclear formation, comprising two structurally equivalent bismuth atoms and three structurally different dithiocarbamate groups. The polymorphs I and II were found to be interconvertible by altering the solvent system during the recrystallisation process. Sun et al. (2012) has reported a crystalline form of the title compound which resembles, but is not identical with, polymorph II. Experimental solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR spectra of both polymorphs I and II were in accord with the direct structural data on these complexes. Assignments of the resonance lines in the solid-state 13C and 15N NMR spectra were assisted by chemical shift calculations of the crystals using periodic DFT.

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Series: Polyhedron
ISSN: 0277-5387
ISSN-E: 1873-3719
ISSN-L: 0277-5387
Volume: 129
Pages: 123 - 132
DOI: 10.1016/j.poly.2017.03.018
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: The current project is financed by the Center for Advanced Mining and Metallurgy (CAMM) at Luleå University of Technology (LTU), Sweden, the Nordic Mining School and Svenska Kulturfonden at the University of Oulu, Finland and the Academy of Finland (#218191, #255641, and #285666). We thank the foundation in memory of J. C. and Seth M. Kempe and LTU labfonden for a grant from which the 400 MHz equipment has been purchased.
Academy of Finland Grant Number: 218191
Detailed Information: 218191 (Academy of Finland Funding decision)
255641 (Academy of Finland Funding decision)
285666 (Academy of Finland Funding decision)
Copyright information: © 2017 Elsevier Ltd. All rights reserved. Published in this repository with the kind permission of the publisher.