An innovative class of ligand compounds using The ions of transition metals (Cr(III), Fe(III), and Ni(II)).The ligand N,N'-(4H-1,2,4-triazole-3,5-diyl)bis(4-methoxybenzamide) was produced by reacting 2,5-di amino-1,2,4-triazole with two moles of methyl 4-methoxybenzoate in the presence of ethanol and a few drops of glacial acetic acid. The recently produced chemicals were studied using a battery of analytical tools, analysis of elements (C, H, and N), nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, mass spectrometry, and atomic absorption are some of the techniques that are included. The aforementioned diagnostic procedures led to the formation of ligand-containing octahedral complexes with (Fe and Cr) ions and a square planer complex with nickel.&nbsp

Natheil, Amal Hussein

English

European Journal of Theoretical and Applied Sciences

  This work is licensed under a Creative Commons Attribution 4.0 International License. The license permits unrestricted use, distribution, and reproduction in any medium, on the condition that users give exact credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if they made any changes.     Synthesis and Characterization New 1, 2, 4-Triazole Derivative  and Its Complexes with Some Transition Metal Ions Amal Hussein Natheil Department of Pharmaceutical Chemistry, College of Pharmacy, University of Thi-Qar, 64001, Thi-Qar, Iraq  Abstract: An innovative class of ligand compounds using The ions of transition metals (Cr(III), Fe(III), and Ni(II)).The ligand N,N'-(4H-1,2,4-triazole-3,5-diyl)bis(4-methoxybenzamide) was produced by reacting 2,5-di amino-1,2,4-triazole with two moles of methyl 4-methoxybenzoate in the presence of ethanol and a few drops of glacial acetic acid. The recently produced chemicals were studied using a battery of analytical tools, analysis of elements (C, H, and N), nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, mass spectrometry, and atomic absorption are some of the techniques that are included. The aforementioned diagnostic procedures led to the formation of ligand-containing octahedral complexes with (Fe and Cr) ions and a square planer complex with nickel.  Keywords: Synthesis, Characterization,1, 2, 4-Triazole, methyl 4-methoxybenzoate, magnetic susceptibility.  Introduction There has been a critical need to synthesize novel anti-infective chemicals for the purpose of treating illnesses caused by microorganisms due to the alarming global issue of multidrug-resistant germs in recent decades. Numerous medicinally significant compounds, most of which exhibit antibacterial properties, have the 1,2,4-triazole nucleus (Patel, & Parmar, 2010). The broad variety of biological activity shown by organic molecules containing heterocyclic ring structures keeps them in high demand. The structural properties of many bioactive compounds include heterocyclic systems, Examples of such compounds are 1, 2, 4-triazoles, 1, 3, 4-thiadiazoles, and derivatives of these compounds. These molecules have acquired relevance (Naeimi, Safari, & Heidarnezhad, 2007). It is well-known that several medications have triazole and thiadiazole rings in their structures (Lippard, & Berg, 1994). Novel compounds derived from 2-amino-1,3,4-thiadiazoles and 1,2,4-triazole-3-thiones which are heterocyclic compounds, have garnered a lot of interest due to their many desirable biological characteristics, including antibacterial and antifungal effects Mohammad, & Shoukry, (2001) and Sallomi, & Shaheen, (1998), respectively. Anticonvulsant, anti-inflammatory, antitumoral, antioxidant, antitubercular, antiviral, and so on. These findings need further investigation into biological properties of compounds comprising 1, 2, 4-triazole and 1, 3, 4-thiadiazole have been investigated.  Material and Methods  Fluka and B.D.H. Chemicals were the companies that provided the chemicals to the company. The infrared spectra were obtained using a Shimadzu FT-IR-spectrometer device with KBr discs for the generated ligands and CsI Suggested Citation Natheil, A.H. (2024). Synthesis and Characterization New 1, 2, 4-Triazole Derivative and Its Complexes with Some Transition Metal Ions. European Journal of Theoretical and Applied Sciences, 2(5), 579-584.  DOI: 10.59324/ejtas.2024.2(5).55                www.ejtas.com                                                                     EJTAS                    2024 | Volume 2 | Number 5 580  discs for the metal ion complexes. Element analyses were carried out on a Thermofinigan flash. Our flame spectrophotometer—a Shimadzu A-A-500 AFG from Japan with the serial number 23-0932-21-0015 and the following specifications: power-150, voltage-AC110/220V, 50-60 Hz—allowed us to determine the relative amounts of the transition metals in the artificial complexes. 1-H NMR spectra at 500 MHz were captured using the Bruker DRX System AL. At an energy of 70 eV, the HP/MS Model 5973 Network Mass Selective Detector was used in order to record the mass spectra of both the ligand and the complexes. Using the Gouy technique and the Balance Magnetic Susceptibility Model (MSB Auto), magnetic measurements were taken. At room temperature, the complexes' molar conductance in DMSO was measured using an Inolabcond 720 conductivity meter. Preparation of the Ligand (L) To begin the ligand synthesis, 50 ml of ethanol and a few drops of glacial acetic acid were combined with 3.32 g of methyl 4-methoxybenzoate, which had a molecular weight of 0.02 mol. Then, this alcoholic solution was supplemented containing 0.99 g of 3, 5-diamino-1, 2, 4-triazole and 0.01 mol of thiazole. Eight hours of refluxing heat was applied to the reaction mixture. Thanks to TLC, we know the response is complete. After the solvent was largely evaporated at decreasing pressure using a rotary evaporator, For the purpose of obtaining the pure chemical, the product was recrystallized from ethanol and water. With a melting point of (189-190) °C, a physical appearance of yellow crystals, and a yield percentage of 89%. H3COCOOCH3methyl 4-methoxybenzoate+NNHNH2NNH2NNHNHNHN2OCOCH3COOCH3N,N'-(4H-1,2,4-triazole-3,5-diyl)bis(4-methoxybenzamide)4H-1,2,4-triazole-3,5-diamine Figure 1. Preparation of the Ligand  A General Approach to Ligand Complex Preparation The reaction mixture consisted of four millimoles of ligand dissolved in sixty milliliters of absolute ethanol and four millimoles of transition metal salt (CrCl3.6H2O FeCl3, and the dissolution of NiCl2.6H2O in fifty milliliters of heated absolute ethanol. For three hours, the mixture was refluxed. Vacuum evaporation was used to remove the solvent once it cooled. A solution of DMF and ethanol (25-75 v/v) was               www.ejtas.com                                                                     EJTAS                    2024 | Volume 2 | Number 5 581  used to crystallize the precipitate after filtering (Patil, et al, 2011). The complexes that were produced are listed in Table 1 along with their physical characteristics and molecular formulas.  Table 1. Displays the Physical Characteristics and Molecular Formula  of the Resulting Complexes No. Formula M.Wt Color (ᴧm)a M.P. oC Yield%    µeff 1 Ligand 367 Yellow   -------- 189-190 89.0 --------- 2 [Cr(L) Cl2]Cl 529 green 81 206-208 72.2 3.6 3 [Fe(L) Cl2]Cl 525 Black  77 219-221 75.7 2.4 4 [Ni(L) Cl2] 495 Green  32 201-203 85.1 0.2 Note: a= Ω-1 cm2 mol-1 (in DMSO solvent).  Results and Discussion At room temperature, the solid states of the newly synthesized ligands and their complexes exhibit remarkable stability. While most organic solvents won't dissolve the ligands on their own, DMF and DMSO will dissolve the metal complexes they form. Molar Conductance  The complexes' concentrations in 10-3 M DMSO solutions were measured in micrograms. Table 1 displays the values of the molar conductance. It follows that one-chloride ions are present outside the coordination sphere, owing to the fact that the results for Cr (III) and Fe (III) complexes indicate that these complexes are electrolytes with a ratio of 1:1. However, the values of the molar conductance (m) are not adequate to indicate the existence of an ionic molecule. thereby ruling out the possibility of an ionic complex; hence, the neutrality of the Ni (II) complex is established. Magnetic Moments The magnetic moments (µeff) of the complexes are shown in Table 1, which has the exact values after they include additional ligands. Complex 1 of iron(III) has a magnetic moment of 2.4 BM, which equates to one unpaired electron (Baluja, Solanki, & Kachhadia, 2006), and its low spin state is likely due to its spin-free octahedral shape. A low spin square planar configuration is based on the magnetic moment of the Ni(II) complex, which is 0.2 BMو With a magnetic moment of 3.6 BM, the Cr(III) complex likely has a spin-free octahedral structure and three unpaired electrons. IR Spectra The generated coordination complexes were identified using the infrared spectra approach. The location of the donor atoms was determined by comparing the spectra with those of the free ligands. The several active groups, including (N-C=O), (C=O), (C=N endocyclic), (NH-endocyclic), (M-N), (M-O), and (M-Cl), were located using the infrared spectra, which also used to identify the ligand. The (N-C=O), (C=O), and (C=N endocyclic) groups are each represented by one of four bands seen in Ligand at (1622) cm-1, (1665) cm-1, and (1573) cm-1, respectively. Furthermore, the presence of bands at (3134) cm-1 and (3211) cm-1 suggests the production of (C-H aromatic) and (NH endocyclic) bands, respectively. In metal complexes of ligands, certain frequencies that are stretching of the (C=N), (N-C=O), and (NH endocyclic) groups are reduced and transferred to reduced frequency ranges of roughly (12-45) cm-1. This occurs because the ligands are attached to the metal, whereas the stretching frequencies of the (CH aromatic) and (C=O) groups are also diminished but do not change (Anatheil, Gatea, & Abdulredha, 2024); This is because these groups are unable to coordinate with metal ions, which is the reason why, this is the result.  The areas (515-540) cm-1, (552-586) cm-1, and (210-308) cm-1 show new bands that indicate coordination as (M-N), (M-O), and (M-Cl), respectively (Anatheil, Gatea, & Neamah, 2024). It can be seen in Figures 1 and Table 2               www.ejtas.com                                                                     EJTAS                    2024 | Volume 2 | Number 5 582  that the nitrogen and oxygen atoms that are present in the ligand's (C=N) and (C=O) groups have collaborated  Table 3. FT-IR Spectra of Ligand and Complexes Compound N-C=O C=O C=N endocyclic NH endocyclic C-H aromatic M-N M–O M–Cl ligand 1622 1665 1573 3211 3134 ----- ----- ---- Cr-L 1606 1666 1566 3198 3134 524 578 210 Fe-L 1608 1665 1528 3178 3133 539 567 287 Ni-L 1614 1665 1564 3169 3134 522 552 308  1H NMR Spectra  At 9.9 ppm, the ligand's distinctive signals from the (-NH-endocyclic) proton are seen in the 1H NMR spectrum. Furthermore, two protons belonging to the (-NH) groups for the ligand may be responsible for the development of the band at 6.8 ppm. Both the ligand and aromatic ring protons may be represented by the band at 3.5 ppm, while the band at 7.5-8.4 ppm might be the other possible candidate (Sekerci, & Tas, 2000).  Mass Spectra Mass spectra of ligand  The scheme (1) incorporates an occurrence of the molecular ion peak, denoted by the symbol M+, the base peak, and a succession of peaks into the ligands' spectra (table 3).  NNHNHNHNOCOCH3COOCH3NNHNHNNHOCH3CO+ OC OCH3CH3O CO+NNHNHNNHNNNHN+NH2OC++OCH3NNHNHNOC+HNOC OCH3NNHNH3CO+OCH3CNONHOC+OCH3H3COm/z= 367.13m/z=232.22m/z=97.08m/z=82.12m/z=104.32m/z=217.22107.14m/z=77.11m/z=96.13m/z=68.07 Figure 2. Important Peaks of Mass Spectrum for Ligand               www.ejtas.com                                                                     EJTAS                    2024 | Volume 2 | Number 5 583   Table 3. Significant Peaks in the Ligand Mass Spectrum No. Fragmentation m/z 1 C18H17N5O4 (Molecular ion) 367 2 C10H10N5O2 232 3 C10H9N4O2 217 4 C7H8O 107 5 C2H3N5 97 6 C6H7O 96 7 C2H2N4 82 8 C6H5 (base peak) 77 9 C2H2N3 68  Mass Spectra of Cr-L The peak of the molecular ion (M+], base peak, and other significant peaks in the Cr-L spectrum are indicative of lost chloride atoms, which are incorporated in the break up (table 4).  Table 4. Significant Cr-L Peaks  in the Mass Spectrum No. Fragmentation m/z 1 [Cr(L) Cl2]+.Cl 525 2 [Cr(L) Cl2]+. 489 3 [Cr(L) Cl]+. 454 4 [Cr(L)]+. 418  Mass Spectra of Fe-L The peak of the molecular ion [M+], base peak, and other significant peaks in the Fe-L spectrum are associated with lost chloride atoms, which are incorporated in the break up (table 5).  Table 5. Fe-L Mass Spectrum's Significant Peaks No. Fragmentation m/z 1 [Fe(L) Cl2]+.Cl 529 2 [Fe(L) Cl2]+. 493 3 [Fe(L) Cl]+. 458 4 [Fe(L)]+. 422  Mass Spectra of Ni-L The peak of the molecular ion (M+], base peak, and other significant peaks in the Ni-L spectrum are indicative of lost chloride atoms, which are incorporated in the break up (table 6).  Table 6. Significant Ni-L Mass Spectrum Peaks No. Fragmentation m/z 1 [Ni(L) Cl2]+. 496 2 [Ni(L) Cl]+. 460 3 [Ni(L)]+. 425  Analysis of Elemental Composition The examination of the elements (C.H.N.S) was used to determine the purity of the ligand, and the results are presented in table (7).  Table 7. Component Analysis of the Ligand that has been Synthesized Ligand  Founded % Calculated % C18H17N5O4 H% C% N% H% C% N% 4.13 58.55 20.31 4.66 58.85 19.06  Conclusions Liquid and complex structures are determined by molar conductivity, magnetic moments, spectroscopy of the infrared spectrum, element analysis, spectroscopy of the H1-NMR spectrum, mass spectroscopy, and molar elements; octahedral configurations are observed in chromium and iron complexes, while square plainer configurations are observed in nickel complexes.  References Anatheil, A. H., Gatea, A. H., & Abdulredha, W. S. (2024). Evaluation of antimicrobial properties of new heterocyclic compounds synthesized               www.ejtas.com                                                                     EJTAS                    2024 | Volume 2 | Number 5 584  from pyrazole. Asian Journal of Medical and Natural Sciences, 5(3), 406–414. Anatheil, A. H., Gatea, A. H., & Neamah, F. O. (2024). Synthesis and biological activity of some new Schiff base metal complexes derived from 2-hydroxybenzaldehyde. Journal of Medical and Pharmaceutical Chemistry Research, 6, 1149–1166. Baluja, S., Solanki, A., & Kachhadia, N. (2006). Synthesis and antibacterial activity of Schiff bases derived from 2-aminobenzothiazole. Journal of the Iranian Chemical Society, 3(4), 312–317. https://doi.org/10.1007/BF03246227  Dede, B., Karipcin, F., & Cengiz, M. (2009). Synthesis, characterization, and antimicrobial activity of mixed ligand copper(II) complexes of Schiff bases derived from salicylaldehyde and amino acids. Journal of Chemical Sciences, 121(2), 163–171. https://doi.org/10.1007/s12039-009-0024-z  Farina, Y., Shaker, S. A., & Salleh, A. A. (2009). Corrosion inhibition of mild steel in acidic solution by using dithiocarbamate. European Journal of Scientific Research, 33, 702–709. Lippard, S. J., & Berg, J. M. (1994). Principles of bioinorganic chemistry. University Science Books. Mohamed, G. G., Omkar, M. M., & Hindy, A. M. (2006). Synthesis, spectroscopic and thermal analysis of some transition metal complexes with Schiff base ligand derived from 2-aminobenzothiazole. Turkish Journal of Chemistry, 30, 361–382. Mohammad, M. M. A., & Shoukry, M. M. (2001). Structural and spectral studies on complexes of some divalent transition metal ions with Schiff bases. Polyhedron, 21(2), 167–173. https://doi.org/10.1016/S0277-5387(01)00815-4  Naeimi, H., Safari, J., & Heidarnezhad, A. (2007). One-pot synthesis of Schiff bases in the presence of acidic ionic liquids. Dyes and Pigments, 73, 251–253. https://doi.org/10.1016/j.dyepig.2005.12.001  Patel, I. J., & Parmar, S. J. (2010). Synthesis, characterization, and antimicrobial activities of some new Schiff bases. E-Journal of Chemistry, 7(2), 617–623. https://doi.org/10.1155/2010/369684  Patil, A. R., Donde, K. J., Raut, S. S., Patil, V. R., & Lokhande, R. S. (2012). Synthesis and antimicrobial activity of some new 2-amino-4,6-diaryl pyrimidines. Journal of Chemical and Pharmaceutical Research, 4(2), 1413–1425. Patil, A. R., Donde, K. J., Raut, S. S., Patil, V. R., & Lokhande, R. S. (2011). Synthesis and antimicrobial activity of some new benzimidazole derivatives. Journal of Pharmaceutical Research, 4(7), 2256–2260. Sallomi, I. J., & Shaheen, A. J. (1998). Spectral, thermal, and structural studies of Co(II), Ni(II), Cu(II), and Zn(II) complexes with a Schiff base derived from o-phenylenediamine and salicylaldehyde. Polyhedron, 19(11-12), 1429–1433. https://doi.org/10.1016/S0277-5387(98)00012-6  Sekerci, M., & Tas, E. (2000). Synthesis, characterization, and antimicrobial activity of some Schiff bases derived from salicylaldehyde. Heteroatom Chemistry, 11, 254–260. https://doi.org/10.1002/(SICI)1098-1071(2000)11:3<254::AID-HC7>3.0.CO;2-0  Souza, P., Garcia-Vazquez, J. A., & Masaguer, J. R. (1985). Synthesis and characterization of mixed-ligand complexes of copper(II) with Schiff bases and heterocyclic bases. Transition Metal Chemistry, 10(5), 410–412. https://doi.org/10.1007/BF01023629   

Synthesis and Characterization New 1, 2, 4-Triazole Derivative and Its Complexes with Some Transition Metal Ions

https://ejtas.com/index.php/journal/article/download/1195/856

Synthesis and Characterization New 1, 2, 4-Triazole Derivative and Its Complexes with Some Transition Metal Ions

Abstract

Similar works

Full text

Available Versions

European Journal of Theoretical and Applied Sciences