Abstract
AbstractWe 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.
Highlights
There has been growing interest in bismuth(III) biocoordination chemistry,[1,2,3,4,5] in the light of the applications of bismuth compounds in pharmaceutical industry, especially, in the treatment for cancer,[6] gastrointestinal diseases,[7] as antimicrobial agent,[8,9] in cosmetic industry,[10] etc
Crystal structure was determined for complex (3), i. e. tris (N,N’-cyclo-pentamethylenedithiocarbamato)bismuth(III), [Bi2{S2CN(CH2)5}6 H2O]; crystallographic data for complex (3) is given in Table 1 and selected geometric parameters are collected in Tables 2 and 3
The 13C and 15N CP-MAS NMR spectra of complex (2) show very distinctive signals for dithiocarbamate and PHEN ligand atoms. Both dithiocarbamate carbon and nitrogen atoms show two well-resolved resonance lines, with an integral ratio of 1 : 1, indicating the presence of at least two inequivalent dithiocarbamate ligands in the asymmetric part of the unit cell, which is consistent with the crystal structure of the complex
Summary
There has been growing interest in bismuth(III) biocoordination chemistry,[1,2,3,4,5] in the light of the applications of bismuth compounds in pharmaceutical industry, especially, in the treatment for cancer,[6] gastrointestinal diseases,[7] as antimicrobial agent,[8,9] in cosmetic industry,[10] etc. In spite of having those advantages, there has been very limited study of Bi(III) dithiocarbamate complexes using the experimental ss-NMR[46,48,49,50] or quantum mechanical modelling and molecular property calculations.[46] This article attempts to fill that research gap by following a multidisciplinary approach for molecular structure and property calculations wherein the results from experimental ss-NMR, X-ray crystallography, and density functional theory (DFT) methods are compared and complemented This combination is often referred to as “NMR Crystallography” methods, which has gained interests of many researchers in organic, inorganic, and in biomolecular disciplines.[57,58,59,60,61]. Building upon our recent studies of heavy metal coordination complex crystals by such an “NMR crystallography” investigation,[46,68,69] we present here the application of this approach to three other bismuth crystals
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