CC BY
24
ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 4 2022 ISSN 0005-2531 (Print)
UDC 546.56: 546.131: 661.725.844.1: 547.583.44
SYNTHESIS AND ANALYSIS OF COORDINATION COMPOUNDS OF NICKEL(II) ACETATE WITH MONOETHANOLAMINE AND p-NITROBENZOIC ACID
A A A A A
B.T.Ibragimov, Sh.B.Khasanov , O.I.Khudoyberganov , Z.Sh.Abdullaeva , E.U.Eshchanov
Institute of General and Inorganic Chemistry, Tashkent Khorezm Mamun Academy, Khiva **Urgench State University, Republic of Uzbekistan, Urgench
zubayda.abdullayeva.91@mail.ru
Received 13.07.2022 Accepted 18.08.2022
This article clarifies the synthesis of a complex combination of p-nitrobenzoic acid with Ni2+ from aromatic carbonic acid derivatives. Moreover, factors influencing the synthesis of the complex compound under room conditions were identified. In particular, the time dependence of the reaction, the effect of temperature, the concentration dependence were studied in practice. The synthesized complex was studied using IR-Fourier spectrometry, elemental analysis, mass spectrometry, TG-DSK and X-ray structural analysis, its chemical structure was determined, and this new complex was proved to be thermally and chemically stable.
Keywords: p-nitrobenzoic acid, nickel (II) acetate, monoethanolamine, complex compound, metal complex, X-ray structural analysis, element analysis, antimicrobial, monocrystal.
doi.org/10.32 73 7/0005-2531-2022-4-43-47
Introduction
One of the pressing issues was to provide the population with a variety of food products, nearly at all stages of human development. In this process, one of the key factors is the rational protection of plants from harmful organisms (pests, diseases and weeds). Protection of plants from pests is very crucial in the cultivation of grain products, potatoes, fruits, vegetables and other crops, as well as, breeding livestock in our country. The main reason for this is that the conditions of Uzbekistan (hot climate, its geographical location and soil conditions) are very favorable for the growth of pests. They find plenty of food and a comfortable place to live in fields, which in turn causes more damage to crops. It should be noted that in Uzbekistan one of the main pests in cotton fields is spider mites (Tetranychidae) gives up to 18-20 generations, while caradrina 4-6, bollworm 3-4, plant lice 16-17 and in potato growing areas Colorado worm 3-4 generations. Therefore, in our conditions, the development and effective use of specific methods of pest control is one of the
most important measures to increase productivity [1-6].
In this regard, in the fight against plant pests include simple monocycles of benzoic acid - all types of isomers of nitro-, amino- and hydroxybenzoic acids (primary ligand), and as auxiliary ligands to obtain mono, di and tri ethanolamines with similar bioactivity. It is advisable to use complex compounds that form them with biometals such as Cu, Co, Mn, Mo and Ni. Because these newly synthesized complexes have antimicrobial and stimulant properties [7].
This work is also devoted to the synthesis and study antimicrobial and stimulating properties of a complex compound of nickel (II) acetate with monoethanolamine and p-nitrobenzoic acid.
Experimental part
Material and methodology
The aim of the work is to develop a method for the synthesis of a complex of Ni (II) acetate with p-nitrobenzoic acid and monoethanolamine, as well as, to study the
composition and structure of the synthesized complex by modern physicochemical methods.
The amount of metal in the synthesized complex was determined on the Novaa 300 apparatus of Analytic Jena (Germany), and the analysis of carbon, hydrogen and nitrogen elements was determined on the "EA 1108" apparatus of Carlo-Erba (Italy). The IQ spectra of the compound were obtained, in the area of 400-4000 cm-1 by IRAffinity-lS spectropho-tometer of the firm Shimadzu (Japan) samples were prepared with KBr tablets with a diameter of 7 mm. X-ray structural analysis was obtained on an Xcalibur Oxford Diffraction automatic diffractometer at a temperature of 293 K (CuKa radiation, k = 1.54184 A, xscan mode, graphite monochromator).
Synthesis methodology
The complex was synthesized according to the following method: 0.002 mol of p-nitrobenzoic acid was dissolved in 20 ml of hot ethanol and it was placed in a round three-mouth- bottom-flask and fixed on a tripod on magnetic stirrer. A thermometer is attached to the left mouth of the flask, a return cooler is attached to the center mouth, and a drip funnel
is attached to the right mouth. The reaction temperature was controlled using a thermometer (optimal reaction temperature t = 45-50 oC). The time to start the reaction was clearly set. A solution of 0.001 mol of nickel (II) acetate in 30 ml of water was then added to a 5 ml solution of ligand in a flask every 5 minutes using a dropper funnel [8-10].
Two hours after the start of the reaction, a 1:30 alcohol solution of monoethanolamine was added to the mixture. The mixture was stirred at 45-500C in a MS-H280-Pro brand magnetic stirrer for 3 hours. The reaction mixture was then left to crystallize at room temperature. After 7-8 days, the green complex precipitate formed was separated, washed in ethanol, and dried in the open air. Reaction of mixed ligand complex:
Product yield 68 %. [C^rNi^On] green crystalline substance, TL= 178-1800C. Calculated by mass fraction (%): Ni 11.67, N
12.6, C 42.54, H 5.16. Found (%): Ni 11.49, N 12.2, C 42.38, H 5.11.
The structure of the obtained compound was analyzed by X-ray and it was determined that it has the following structure (Figure 1).
Fig. 1. Structure of complex molecules of compounds [Ni(MEA)3)(PNBK)]*2H2O
Hence, in the mononuclear [Ni(MEA)3)(PNBK)]-2H2O complex, Ni2+ ions are located at the center of inversion. It is coordinated with three molecules of MEA molecules by oxygen atoms in the amino group - nitrogen and hydroxyl group [11-17].
Thus, a complex molecule is a complex ion with a charge of +2, which requires the placement of a component with a negative charge in the outer sphere to compensate for the positive charge. These are two crystallogra-
phically independent p-nitrobenzoate ions in the form of benzoate. The image also shows 2 molecules of water outside the structure. When the lengths and angles of the valence bonds were analyzed using the MOGUL program adapted to the MERCURY complex, it was found that there were no bonds and angles with non-standard values between them.
Its TG-DSK analysis also proves that the synthesized complex is a new compound [18-19].
TG/% DSC/(mVWmg)
Peak 168 9*C Peak 22Z3 *C texo
Temperatire TC
Fig. 2. TG-DSK analysis of the synthesized complex compound.
Conclusion
The [Ni((PNBK)2(MEA)3)] complex consists of Ni (II), PNKB, and MEAs, and a mixed ligand compound with a 1: 2: 3 content. The complex molecule contains OH- and NH2-groups that can act as donors in hydrogen bonds. When the hydroxyl group only participates as a donor in the internal hydrogen bond, the two hydrogen atoms of nitrogen in the MEA form intermolecular hydrogen bonds with the oxygen atoms, leading to the formation of x-axis-oriented columns. Oxygen atoms of the nitro group do not participate in the formation
of hydrogen bonds. The relatively large distance between the centroids of the parallel aromatic nuclei indicates that there is no significant stacking effect of 4,781 A. Therefore, only a pair of hydrogen bonds of the amino and hydroxyl groups of MEA are involved in the formation of the crystal structure. It also forms columns oriented along the x-axis [20].
The structure of the obtained compound was analyzed by IR and it was determined that the following absorption areas were present (Figure 3).
MIRaclel 0 (Dia/ZnSe) cm-1
Figure 3. IR spectra of the synthesized complex compound.
References
1. Kimsanboev X.X., Yuldashev A.Y., Zohidov M., Khalilov K.X. Chemical protection of plants. Tashkent: Teacher, 1997. P. 3-20.
2. Aliyeva F.S., Mamedova F.O., Yusifov Y.E., Chi-ragov F.M. Synthesis and structure of bis-[3-(fluorphenylazo- pentadiene-2,4)ethylenediimines] and the study of complex formation with cop-per(II) ion. Azerb. Chem. J. 2020. No 2. P. 56-60.
3. West D.X., Liberta A., Padhye S.B., Chikate R.C., Sonawane P.B., Kumbhar A.S., Yerande R.G. Thi-osemicarbazone complexes of copper(II): structural and biological studies. Coord. Chem. Rev. 1993. No 123. P. 49-71.
4. Nassar A.M., Hassan A.M., Elkmash A.N. Synthesis, characterization, corrosion inhibition of mild steel in HCl (0.5 N) solution and solid-state electrical conductivity of new Co(II), Ni(II), Cu(II) and Zn(II) complexes. Appl. Organometal. Chem. 2016. No 31(3). P. 1-9.
5. Firdausa F., Fatmaa K., Azama M., Khanb S.N., Khanb A.U., Shakir M. Template synthesis and physico-chemical characterization of Synthesis and characterisation of Co(II), Ni(II), Zn(II) and Cd(II) complexes 14-membered tetraimine macro-cyclic complexes, [MLX2] [M=Co(II), Ni(II), Cu(II) and Zn(II)]. DNA binding study on [CoLCl2] complex. Spectrochim Acta Part A. 2009. No 72. P. 591-96.
6. Shakir M., Khanam S., Azam M., Aatif M., Fir-daus F. Template synthesis and spectroscopic characterization of 16-membered [N4] Schiff-base macrocyclic complexes of Co(II), Ni(II), Cu(II), and Zn(II): in vitro DNA-binding studies. J. Coord. Chem. 2011. No 64. P. 3158-68.
7. Ibragimov A.B. Synthesis, structure and biological activity of metal and supramolecular complexes based on p-nitrobenzoic acid and ethanolamines. Doctor of Philosophy in Chemistry. ... dis. Tashkent: Institute of General and Inorganic Chemistry, 2017. 120 p.
8. Ibragimov A.B., Ashurov Zh.M., Ibragimov A.B., Tashpulatov Zh.Zh. Synthesis, Structure, and Fungicidal Activity of Mono- and Binuclear Mixed-Ligand Copper Complex with p-Nitro-benzoic Acid and Monoethanolamine. Russian J. Coordin. Chemistry. 2017. No 43 (6). P.380-388.
9. Majid K., Mustaq R., Ahmad S. Synthesis, Characterization and Coordinating Behaviour of Ami-noalcohol Complexes with Transition Metals. E-Journal of Chemistry. 2008 No.5. P. 969-979.
10. Ahmed A., Abu-El-Halawa R., Zabin S.A., Mohammad I., Mahmoud A.R., Tawfeq K. Synthesis, Characterization and Antifungal Activity of Some Metal Complexes Derived From Quinoxaloylhy-drazone. World J. Org. Chem. 2015. No.3. P.1-8.
11. Kiselev Yu.M. Chemical coordination of compounds. Textbook and assignment for bachelors and masters. M.: Yurayt, 2014. 657 p.
12. Len J.-M. Supramolecular chemistry. Concepts and perspectives. - Novosibirsk: Nauka, 1998. p. 344.
13. Mortikov V.Yu., Litvinov V.P., Shestopalov A.M., Sharanin Yu.A., Apenova E.E., Galegov G.A., Abdullaev I.I., Asadullaev T.B., Abdullaev F.I. Synthesis and antiviral activity of 3-cyano-2(1H)pyridine selenones. Pharmaceutical Chemistry Journal. 1991. No. 25. p.312.
14. Nakata B., Yamagata S., Kanehara I., Shirasaka T., Hirakawa K. Translating, a cisplatin transisomer, may enhance the anticancer effect of 5-fluorouracil. J. Exp. Clin. Cancer Res. 2006. No 25(2). P.195-200.
15. Frolov Yu. Nobel Prizes 2001. Science and life. 2002. №1.
16. Groom C. R., Allen F. H. The Cambridge Structural Database in Retrospect and Prospect. Chem. Int. Ed. 2014. No 53. P. 662- 671.
17. Khudoyberganov O., Ruzmetov A. , Ibragimov A., Ashurov J., Khasanov Sh., Eshchanov E., Ibragimov B. Synthesis, crystal structure and Hirshfeld surface analysis of the binuclear Cu(II) complex with 4-nitrobenzoic acid and triethano-lamine. Chemical Data Collections. 2022. doi.org/10.1016/j.cdc.2021.100802
18. Almyashev V.I., Vasilevskaya A.K., Kirillova S.A., Krasilin A.A., Proskurina O.V. Complex thermal analysis. Under the editorship of V.V. Gusarova. M.: Lema. 2017. P. 61 - 83.
19. Gabbott P. Principles and Applications of Thermal Analysis. Singapore, Wiley-Blackwell, 2008. 480 p.
20. Abdullayeva Z.Sh., Kadirova Sh.A., Khasanov Sh.B., Eshchanov E.U. Coordination compounds of copper (II) formate with sodium and barium acetates. J. Critical Reviews. 2020. №7. P. 480-481.
MONOETANOLAMiN VO P-NiTROBENZOY TUR§USU iLO NiKEL(II) ASETATIN KOORDiNASiYA
BiRLOSMOLORiNiN SiNTEZi VO TOHLiLi
B.T.ibrahimov, ^.B.Hasanov, O. i.Xudayberqanov, Z.§.Abdullayeva, E.U.Eschanov
N-nitrobenzoy tur§usunun Ni2+ ila karbondioksidin aromatik birla§malarindan kompleks birla§masinin sintezi 6yranilmi§dir. Otaq §araitinda kompleks birla§manin sintezina tasir edan amillar muayyan edilmi§dir. Xususila reaksiyanin vaxtdan, temperatur tasirlarindan, konsentrasiyadan asililigi praktiki olaraq tadqiq edilmi§dir. Sintez olunmu§ kompleks birla§ma IQ Furye-spektrometriya, element analizi, kutlavi spektrometriya, tg-DSK va rentgenoqrafik analiz metodlanndan istifada etmakla 6yranilmi§ va onun kimyavi strukturu muayyan edilmi§, hamginin bu yeni kompleks birla§ma istilik va kimyavi cahatdan sabit olmu§dur.
Agar sozlzr: p-nitrobenzoik tur§usu, nikel asetati (II), monoetanolamin, kompleks birh§m3, Metalkompleks, rentgenstruktur analizi, element analizi, antimikrob vasit3, monokristal.
СИНТЕЗ И АНАЛИЗ КООРДИНАЦИОННЫХ СОЕДИНЕНИЙ АЦЕТАТА НИКЕЛЯ(П) С МОНОЭТАНОЛАМИНОМ И p-НИТРОБЕНЗОЙНАЯ КИСЛОТА
Б.Т.Ибрагимов, Ш.Б.Хасанов, О.И.Худайберганов, З.Ш.Абдуллаева, Э.У.Эшчанов
Из состава ароматических карбонных кислот изучен синтез комплексного соединения p-нитробензойной кислоты с Ni2+. Определены факторы, воздействующие синтезу комплексных соединений при комнатных условиях. В частности, на практике исследованы: зависимость реакции от времени, воздействие температуры, зависимость от концентрации. При помощи способов IQ-Фуре-спектрометрия, анализ элемента, масс-спектрометрия, TG-DSK и рентгенского структурного анализа изучилось синтезированное комплексное соединение, определен его химический состав, а также была доказана термическая и химическая устойчивость этого нового комплесного соединения.
Ключевые слова: р-нитробензойная кислота, никель (II) ацетат, моноэтаноламин, комплексное соединение, комплекс металла, рентгеновский структурный анализ, анализ элемента, антимикроб, монокристалл.
