The use of Optical Microscopy, X-ray Powder Diffraction, and Single Crystal Diffraction to Identify and Structurally Characterize Novel Transition Metal Benzoates.

  • Motunrayo Ladele

Student thesis: Phd


This research investigated medium scale synthesis and crystallization, followed by structural characterization, as a means of discovering new solid‐state products, with a series of controlled micro‐scale reaction/crystallization experiments using various reagent ratios whilst monitoring changes using optical microscopy. By characterizing any crystals formed, the products (monomers, dimers, polymers, clusters, solvates, and polymorphs) were mapped in terms of reaction conditions (reagent ratios, solvent, temperature, time in solution). Chapter 1 of this thesis covers the coordination polymer of 1st-row 3d transition metals and substituted benzoic acids. (1D, 2D, and 3D). Chapter 2 describes the theory and practice of X-ray single crystal diffraction. Chapter 3 describes the crystallization reaction of the substituted benzoic acids such as HOC6H3-1,3-(CO2H)2, H2NC6H3-1,3-(CO2H)2, (HO)2C6H2-1,4-(CO2H)2, C6H4-1,4-(CO2H)2 and C6H4-1,3-(CO2H)2 with a range of 1st-row 3d transition metal halide/acetate such as CuCl2, CoCl2.6H2O, ZnCl2, FeCl2, VCl3, NiCl2, CoCl2 and Zn(CH3COO)2.2H2O in H2O and in 50:50 H2O/MeOH. These metal-ligand reactions produced known [Zn(C8H5NO4)(H2O)]n, [Co(C8H4O6)(Me2NCHO)2(H2O)2]n and unknown (C8H6O6).2(Me2NCHO) metal complexes that were investigated using optical microscopy and single crystal X-ray diffraction. Chapter 4 describes the small-scale crystallization of MSO4 hydrates, where M = Cu, Co, Zn, and Ni (as a pure metal and as a bimetallic reaction) with sodium 2-amine-3-methybenzoate (NaAMB) from aqueous solution in order to screen for mixed metal compounds, polymorphs, and solvates. These pure and bimetallic metal-ligand reactions produced known and unknown hydrate and anhydrous metal complexes: [Cu(C8H8NO2)2]n, [Cu(C8H8NO2)2.2H2O]2, {Cu(C8H8NO2)2]2.8/3H2O}n, {Cu(C8H8NO2)2]2.13/5H2O}n, [Zn(C8H8NO2)2]n, {Co(C8H8NO2)2}n, {Co(C8H8NO2)2.H2O}n and [Ni(C8H8NO2)2(H2O)2].2H2O. Chapter 5 describes the small-scale crystallization of MnSO4 and MnCO3 hydrates with benzoic acid from aqueous solution to screen for polymorphs and solvates. These reactions produced two manganese benzoate linear chain polymers [Mn2(C6H5CO2)4(H2O)6].[H2O)2 and {Mn2(C6H5CO2)4(H2O)4}n. Chapter 7 concludes the thesis and suggests further work.
Date of Award31 Dec 2019
Original languageEnglish
Awarding Institution
  • The University of Manchester
SupervisorFrancis Mair (Supervisor) & Robin Pritchard (Supervisor)

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