University of Oulu

V. Gowda, B. Sarma, A.-C. Larsson, P. Lantto, O. N. Antzutkin, ChemistrySelect 2020, 5, 8882.

Bi(III) complexes containing dithiocarbamate ligands : synthesis, structure elucidation by X‐ray diffraction, solid‐state ¹³C/¹⁵N NMR, and DFT calculations

Saved in:
Author: Gowda, Vasantha1,2; Sarma, Bipul3; Larsson, Anna-Carin1;
Organizations: 1Department of Civil, Environmental and Natural Resources Engineering, Chemistry 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 Chemical Sciences, Tezpur University, Tezpur-784028, India
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 1.2 MB)
Persistent link:
Language: English
Published: John Wiley & Sons, 2020
Publish Date: 2020-08-21


We report on syntheses, characterisation by nuclear magnetic resonance (NMR) spectroscopy, X‐ray diffraction (XRD) measurements, and density functional theory (DFT) calculations of electronic/molecular structure and NMR chemical shifts of complexes of Bi(III), having the molecular formulae: [Bi{S₂CN(C₂H₅)₂)}₃] (1), [Bi{S₂CN(C₂H₅)₂)}₂(C₁₂H₈N₂)NO₃)] (2), and [Bi₂{S₂CN(CH₂)₅}₆ • H₂O] (3). The powder XRD patterns of complexes (1) and (2) resembled the corresponding calculated powder XRD patterns for previously reported single crystal structures. Single crystal XRD structure of complex (3), reported in this work, adopted an orthorhombic system with a space group Pbca with a=10.9956(3) Å, b=27.7733(8) Å, c=35.1229(10) Å and α=β=γ=90°. The experimental solid‐state ¹³C/¹⁵N NMR data of the complexes (1)‐(3) were in accord with their X‐ray single crystal structures. The unit cell of the complex (3) shows a weak supramolecular Bi···S interaction leading to the formation of a non‐centrosymmetric binuclear molecule [Bi₂{S₂CN(CH₂)₅}₆ • H₂O], which displays structural inequivalence in both ¹³C/¹⁵N NMR, and XRD data. Assignments of resonance lines in solid‐state ¹³C/¹⁵N NMR spectra of complexes (1)‐(3) were assisted by chemical shift calculations using periodic DFT methods. The findings of the present multidisciplinary approach will contribute in designing molecular models and further understanding of the structures and properties of (diamagnetic) metal complexes, including heavy metal ones.

see all

Series: ChemistrySelect
ISSN: 2365-6549
ISSN-E: 2365-6549
ISSN-L: 2365-6549
Volume: 5
Issue: 29
Pages: 8882 - 8891
DOI: 10.1002/slct.202001692
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 (CAMM²) at Luleå University of Technology (LTU), Sweden, and Nordic Mining School and Svenska Kulturfonden at University of Oulu, Finland, and Academy of Finland (#218191, #255641, and #285666). Additional financial support has been obtained from the University of Oulu (Kvantum Institute). We thank the foundation in the memory of J. C. and Seth M. Kempe and LTU labfonden for a grant from which the 400 MHz NMR 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: © 2020 The Authors. Published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.