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Bi(III) Complexes Containing Dithiocarbamate Ligands: Synthesis, Structure Elucidation by X‐ray Diffraction, Solid‐State 13 C/ 15 N NMR, and DFT Calculations
Author(s) -
Gowda Vasantha,
Sarma Bipul,
Larsson AnnaCarin,
Lantto Perttu,
Antzutkin Oleg. N.
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202001692
Subject(s) - crystallography , orthorhombic crystal system , crystal structure , density functional theory , chemistry , nuclear magnetic resonance spectroscopy , nmr spectra database , solid state nuclear magnetic resonance , single crystal , molecule , chemical shift , nuclear magnetic resonance crystallography , supramolecular chemistry , dithiocarbamate , x ray crystallography , stereochemistry , diffraction , spectral line , computational chemistry , nuclear magnetic resonance , fluorine 19 nmr , physics , organic chemistry , astronomy , optics
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{S 2 CN(C 2 H 5 ) 2 )} 3 ] ( 1 ), [Bi{S 2 CN(C 2 H 5 ) 2 )} 2 (C 12 H 8 N 2 )NO 3 )] ( 2 ), and [Bi 2 {S 2 CN(CH 2 ) 5 } 6 • H 2 O] ( 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 13 C/ 15 N 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 [Bi 2 {S 2 CN(CH 2 ) 5 } 6 • H 2 O], which displays structural inequivalence in both 13 C/ 15 N NMR, and XRD data. Assignments of resonance lines in solid‐state 13 C/ 15 N 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.