American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 313 | P a g e SYNTHESIS AND CHARACTERIZATION OF SOME COMPLEXES WITH IBUPROFENYL HYDRAZONE Amira J. Al_Shaheen Chemistry Department, Education College, Mosul Uni. Mosul E-mail: amiraalshheen@uomosul edu.org Miaad A. Al Mula Chemistry Department, Education College, Mosul Uni. Mosul E-mail: miaadadil@gmail.com ABSTRACT Fourteen new metal complexes have been synthesized from ibuprofenyl hydrazide and vanillin or acetophenone ligands (L1 and L2) and used in preparing the corresponding Cobalt(II) , Nickel(II) , Copper(II) , Zinc(II) , Cadmium(II) complexes. The resulted complexes have been characterized by different physiochemical methods including elemental analyses, IR electronic spectra , magnetic moment measurements , molar conductance, and X-ray powder diffraction measurements, the ligands have been investigated by NMR spectra . Furthermore, the complexes have been found to have the formulas [M(L)2Cl2] where, M= Co(II) , Ni(II) , Cu(II) and Zn(II). whereas, the formula [M(L)2(H2O)2](NO3)2 , M= Co(II) , Ni(II) , [Cd(L)2]Cl2 ; L = L1 or L2 . Infrared spectral data suggest that the two ligands behave as a bidentate ligand with O,N, donor atoms towards the metal ions . Based on the above physicochemical measurements, the complexes have octahedral and tetrahedral geometries. Keywords: X ray powder diffraction, metal complexes and ibuprofenyl complexes. 1. Introduction Ibuprofen is 2-(4- isobutyl phenyl) propionic acid, is a member of non –steroidal anti- inflammatory drug (NSAIDs), known to relief a widely used non steroidal anti- inflammatory drug in treating pain and inflammatory drug (Fiori-Duarte,2019) but the long term use of this effects and nephrotoxicity.This led to the introduction of new compounds of Ibuprofen with an improved profile our aim to develop new safer drugs and improving the pharmacokinetic and pharmacotoxicological profile through complexation (Paulo-Santos et.al 2020). It has been reported that complexes of metallic salts are more potent and less toxic in many cases as compared to the parent drugs. known to relief symptoms of arthritis, primary dysmenorrhea, fever and also possess mild antiplatelet effect ( Ariana,et.al,2022) is useful in sepsis-induced acute pneumonia, in retarding metastases of mammary carcinoma and in preventing oxidative lesions of lungs caused by phosgene. American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 314 | P a g e High doses of ibuprofen slow down the evolution of lung disease. It also protects prostaglandin H synthase of human endothelial cells from hydrogen peroxide (Sondhi,et.al,2006). Hydrazones, a member of the Schiff base family with triatomic >C=N-N< Linkage , takes the fore front position in the development of coordination chemistry. Reports on the synthesis, characterization and structural studies on hydrazone ligands derived from (vanillin and acetophenone) show the importance of hydrazone complexes in various fields including analytical and biological field (Sheikhshoaie & Ebrahimipouret.al,2014). Hydrazone derivatives possessing anti- inflammatory, analgesic, antipyretic and antibacterial activities are also reported in the literature (Kafarska,et.al,2009,Bhandari,et.al.,2008). These complexes which plays an important role in reducing the toxicity of the parent drug and acts as a pro- drug (Abbas,et.,al. 2015, Kafarsk,et.,al. 2009). 2-Experimental: 1. Materials and Measurements : All chemicals and solvent used for the syntheses were of analytical grade, the metal salts were commercially available pure samples and all chemicals used throughout this investigation from Merch ,B.D.H., Aldrich or Fluka and used without further purification. 2. Analytical and physical measurements Melting point and decomposition temperature were determined using Stuart™ melting point apparatus SMP3-England. IR spectra measurements were recorded using FTIR-spectrometer (shimadzu), as ATR-unit in the range (400-4000 cm-1). UV- Visible spectral measurements were recorded using Uv-vis 1900 spectrophotometer (shimadzu) for 10-3 M complexes in DMF solvent at room temperature, using 1cm quarts cell in range (200-900)nm . Elemental analysis were carried out on a Elementar Analasen system GmbH CHNS Germany.The NMR was recorded on Agilant Varian (USA), 500 MHz using deuterated DMSO-d6 as a solvent . Molar conductance of complexes were measured at room temperature for 10-3 M in DMF using (WTW-Cond 3210, Germany). Magnetic susceptibility of the complexes was carried out by (Sherwood Scientific MK 1 Magnetic Susceptibility Balance( at room temperature. Metal contents were estimated spectrophotometrically using atomic absorption spectrometer NOVAA 350 Scientific Equipments. X-ray powder diffraction data for complexes were measured by using XRD - Philips X’PERT powder diffractometer, Holland (University of Kashan- Iran). Preparation of the Ligands and the Complexes: 1. Synthesis of 2(4-isobutyl phenyl) propionic acid ethyl ester (Ibuprofenyl ethyl ester ) (1) The Ibuprofen was esterified (Bhandari,et.al.,2008), by dissolving ( 6.18 g, 0.03 mole) of it in 20 ml of ethanol and then to that 2.0ml of sulfuric acid was added . The mixture American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 315 | P a g e was refluxed for 6-8 hrs. After completion of reaction solvent was removed by add 100m of cold water , followed by extracted with sodium bicarbonate and separated in the organic layer. The yield (80%) , b.p 250-252 oC, empirical formula C15H22O2. %N %H %C -- 9.40 76.92 Calc. -- 9.48 77.01 Found 2. Synthesis of 2-(4-isobutylphenyl) propionoic acid hydazide )(2) The hydrazide was prepared (Abbas,et.,al. 2015), by refluxing (4.68g , 0.02mol) of 2- (4-isobutyl phenyl) ethyl propionate in 15ml ethanol with an excess of hydrazine hydrate NH2. NH2.H2O(85%) for 24h , the reaction mixture was then left to stand overnight .The compound precipitated on standing over night, filtered and washed with cold distilled water. The pure solid white hydrazide was obtained by recrystallization from ethanol, yield (81%), mp 76-78C empirical formula C13H20 N2 O. %N %H %C 12.72 9.09 70.90 Calc. 12.65 9.12 70.00 Found 3. Synthesis of hydrazone ligands (L1 & L2) The ligands synthesized according to the method described in the literature (Hrinath,et.,al. 2011)by reacting equimolar amount of Ibuprofenyl hydrazide and vanillin or acetophenone . A hot ethanolic solution of the ligand made by dissolving ( 2.2g, 0.01 mole) of Ibuprofenyl hydazide in 15 ml of ethanol has been slowly mixed with a hot ethanolic solution containing ( 1.52g , 0.01 mole) of vanillin or acetophenone (1.20g, 0.01 mole). The resulting mixture has been refluxed for about 6 hrs. The mixture has been left to stand for nearly two hours. The precipitated compound was filtered recrystallized from ethanol, washed with ether and dried under vacuum. The structures of the ligands are shown in Scheme 1 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 316 | P a g e Scheme 1: The structures of the ligands Table 1 : physical properties and analytical data of the ligands ligands Empirical formula , M.wt Colour m.p (C) Yield % Elemental analysis calcu. (found) % C % H % N L1 C21H26 N2 O3 354 white 103-104 71% 71.16 (71.21) 7.39 (7.41) 7.90 (8.00) L2 C21H26 N2O 322 white 108-110 79% 78.20 (78.85) 8.07 (8.13) 8.69 (8.72) 4. Synthesis of the complexes According to the following procedure, the complexes were obtained by adding an ethanolic solution of (Baligarand Revankar,2006) metal(II) chloride or nitrate (0.005mol) with the ligand L1 (7.08 gm. , 0.01mol) or L2 (6.44gm , 0.01mol) in the mole ratio 2:1 (L:M) after Mixing, an ethanolic solution has been refluxed for 5hrs . American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 317 | P a g e The volume of the solution was reduced to its half and the precipitated complexes washed with ethanol, followed by diethyl ether and dried in an oven at (70-80) Cº. Table 2: Weight of metal salts used to prepare complexes. Table 3 : Characterization , analytical , molar conductance and magnetic susceptibility data of the complexes . Metal salt Wt(g) metal salt metal salt Wt(g) metal salt CoCl2.6H2O 1.19 CuCl2.2H2O 0.85 Co(NO3)2. 6H2O 1.45 Zn Cl2 0.68 NiCl2. 6H2O 1.18 Cd Cl2 0.91 Ni(NO3)2.6H2O 1.45 N O. Formula Mol. Wei ght Colo r Yie ld m. p (C) º M eff B. M ΛM DM F Cm 2. Oh m1. mol - Calculate( Found )% %C %H %N %M 1 [Co(L1)2Cl2] 838 Ora nge 65 25 2 4. 98 18 60.1 4 (60. 02) 6.2 0 (6.0 9) 6.6 8 (6.6 0) 7.04 (6.9 4) 2 [Co(L1)2(H2O)2 ](NO3)2 927 Ora nge 70 28 2 4.7 5 103 54.3 6 (54.2 1) 6.0 4 (5.9 5) 9.0 6 (8.8 9) 6.36 (6.1 2) 3 [Ni(L1)2Cl2] 737. 7 Ora nge 73 29 5 2. 89 21 60.1 6 (60. 07) 6.2 0 (6.0 9) 6.6 8 (6.4 3) 7.00 (7.0 2) 4 [Ni(L1)2 (H2O)2](NO3)2 926. 7 Bro wn 77 27 9 3. 06 100 54.3 8 (54.1 7) 6.0 4 (5.9 1) 9.0 6 (8.7 9) 6.33 (6.1 7s) 5 [Cu(L1)2Cl2] 842 Gree n 75 23 2 2. 07 25 59.8 5 6.17 6.6 5 7.48 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 318 | P a g e (60. 00) (6.0 7) (6.5 0) (7.3 7) 6 [Zn(L1)2Cl2] 844 Yell ow 77 >3 00 Di a 21 59.71 (60. 00) 6.6 3 (6.4 7) 6.6 3 (6.4 0) 7.70 (7.4 3) 7 [Cd(L1) ]Cl2 891 Yell ow 69 26 3 Di a 97 56.5 6 (56.3 9) 5.8 3 (5.9 6) 6.2 8 (6.0 0) 12.5 7 (12. 35) 8 [Co(L2)2Cl2] 774 Gree n 70 28 8 4. 98 15 67.7 4 (67.5 8) 6.71 (6.5 5) 7.52 (7.2 9) 7.93 (8.0 7) 9 [Co(L2)2(H2O)2 ](NO3)2 863 Bro wn 75 25 3 4. 99 96 58.4 0 (58. 66) 6.4 8 (6.4 1) 9.7 3 (9.9 5) 6.83 (7.0 0) 10 [Ni(L2)2Cl2] 773. 7 Gree n 68 26 4 3.2 8 28 67.7 6 (68. 02) 6.9 9 (7.1 1) 7.52 (7.3 3) 7.89 (8.0 2) 11 [Ni(L2)2(H2O)2 ](NO3)2 862. 7 Gree n 76 20 7 3. 08 115 58.4 2 (58. 67) 6.4 5 (6.5 3) 9.7 3 ( 9.5 0) 6.80 (7.0 3) 12 [Cu(L2)2Cl2] 77.8 Gree n 66 29 0 2.1 5 21 64.7 8 (65. 02) 6.6 8 (7.0 0) 7.19 (7.0 2) 8.09 (7.9 6) 13 [Zn(L2)2 Cl2] 780 Yell ow 64 271 Di a 14 64.6 1 (64. 50) 6.6 7 (6.8 2) 7.18 (7.0 5) 8.33 (8.2 5) 14 [Cd(L2)2] Cl2 829 Yell ow 77 >3 00 Di a 125 60.9 4 (61.o 7) 6.2 8 (6.1 7) 6.77 (6.9 1) 13.5 4 (13. 61) American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 319 | P a g e 5. Results and discussion : Molar conductance values of complexes (1, 3, 5,6,8,10,12 and 13) in 10-3 M DMF are neutral .while complexes (2, 4,9,11 14) are 1:2 electrolytic nature for nitrate and chloride complexes. The molar conductance values and the metal contents are in a good agreement with given formulations (Geary ,1971),(Table 3). 1- Electronic Spectra and magnetic moment Measurements: The electronic spectra of these two ligands L1and L2 and their complexes in DMF solution have been recorded giving ultraviolet spectra, d-d spectra and charge transfer spectra (Table 4 ).The ultraviolet spectra of the ligands exhibited two bands at (30487,36101) cm-1, (27173,27777) cm-1 assigned to n  π* ( C=O) and π π* (C=N) transitions respectively. All these transitions were also found in the spectra of the complexes but they were shifted to lower frequencies confirming the coordination of the ligands to the metal ions (Lever,1968). and these values agree with the magnetic moments obtained for cobalt(II) complexes 1,2,8 and 9 are 4.98,475,4.98 and 4.99 B.M. respectively ,and this values greater than theoretical value (3.87) B.M. due to orbital contribution (Nicholls ,1975,Suttan,1998). The electronic spectra of Co(II) complexes (1,2,8 and 9) exhibit three bands due to ν1 at (11157-13177) cm-1 , ν2 at (14816-15337) cm-1 and ν 3 at (16103-21141) cm-1 which are assigned to following transitions: 4 T1g (F) 4 T2g (F) ν1 7500-11000 cm–1 4 T1g (F) 4 A2g (F) ν2 11000-16000 cm– 4 T1g (F) 4T1g (P) ν3 18000-26000 cm– and these values agree with high spin octahedral configuration. While Ni(II) complexes (3,4,11and12) exhibit electronic spectrum bands at (11235 – 13071)cm-1 , (14104 – 18456) cm-1 and (20576 – 26737) cm-1 respectively , and assigned to transitions : 3 A2g (F) 3 T2g (F) ν1 3 A2g (F) 3 T1g (F) ν2 3 A2g (F) 3 T1g (P) ν3 The octahedral geometry of Ni(II) ion in the complexes is confirmed by the measured magnetic moment values (2.89 – 3.28) B.M.( Mamata,et,al., 2008 and Sutton,1998). The Cu(II) complexes (5 and 12) showed one band at (16780 , 18780) cm-1 respectively . This band may arise from the 2Eg 2E1g , This band has been comparable both in position and width with the reported octahedral complexes , the magnetic moment obtained for these complexes are (2.07 , 2.15) B.M respectively (Baran,2013).(Table4). American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 320 | P a g e Table 4 : Electronic spectra data of the complexes CT = Charg transfer band 2- Infrared Spectra : The IR spectra of the free ligands (L1 and L2) showed band at 2956 cm-1 which is characteristic of stretching vibration (Mitu,et.al,2009) of the NH and other absorption band appeared at (1651, 1620) cm-1 which have been attributed to frequency of C=O amide group . This band in complexes is shifted to lower frequency indicating coordination of carbonyl oxygen atom to the metal (El-Faham,et.al.,2015) .A[so showed a strong band in the region (1589 , 1595) cm-1 , which is characteristic of the azomethine (stretching vibration of (C=N) group .This band in complexes is shifted to lower frequency indicating coordination of azomethine nitrogen atom to the metal (Al- Shaheen and Al-Bergas,2020). The spectra of L1 and L2 showed, a broad band at (1076, 1060) cm-1 due to N-N group shift towards lower frequency on complexation (Al- Shaheen,2017). The aqua complexes contain weak to medium abroad band at (3184 – 3392) cm-1 due to stretching vibration OH of water. Molecules are coordinated, confirmed by occurrence of additional strong band at (821 – 877) cm-1 due to OH rocking vibration (Gamo, 1960,Bellamy,1966 ). The spectra of the complexes showed bands in the region (536 – 628) cm-1 and (403 – 500) cm-1 are assigned to M-O and M-N stretching bands of the metal complexes( Sallomi and AI-Shaheen, 1994), ) In addition the coordination of chloride could not be inferred from infrared spectra of the complexes because the band occurred beyond the range of our infrared spectrophotometer, whereas for Cl- ionic has been checked by AgNO3. Chloride complexes 5 and 14 showed a band at 628 & 648 cm-1 has been attributed to ionic chloride (Cotton. and Wilkinson, 1980) On the other hand, the spectra of some complexes showed the presence of a band at (1373-1384) cm-1 due to ionic nature of nitrato group (Cotton. and Wilkinson, 1980) (Table 5).Fig. 2 and 3. Comp.No. Electronic transition of d-d cm-1 CT ν1 ν 2 ν3 1 13177 14947 16103 33557 2 12297 15337 18103 31645 3 12195 16286 20576 38615 4 112235 14104 26737 35971 5 16780 - - 32607 8 11157 14816 21141 33557 9 13333 16366 20491 36101 10 13071 18456 22123 31446 11 11627 16286 22935 37764 12 18796 - - 31152 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 321 | P a g e Table 5: Selected I.R. bands of the ligands and its complexes (in cm)-1 Comp No.  (N- H)  (O- H)  (C=N)  (N- N)  (C=O)  (M- O)  (M- N) Other L1 2956 3200- 3300 1589 1076 1651 -- -- -- L2 2956 - 1595 1060 1620 -- -- -- 1 2958 3200- 3300 1500 1031 1587 553 426 -- 2 2960 3200- 3300 1500 1022 1583 551 491  IonicNO3 1377, 761 -OH2 3300, 821 3 2958 3200- 3300 1500 1020 1583 525 450 -- 4 2953 3200- 3300 1535 1010 1566 588 422  IonicNO3 1377, 761 -OH2 3300, 821 5 2954 3200- 3300 1581 1018 1581 565 455 -- 6 2958 3200- 3300 1502 1015 1558 588 491 -- 7 2950 3200- 3300 1540 1037 1580 567 470  - ionic Cl -,628 8 2956 -- 1508 1029 1581 524 504 -- 9 2954 -- 1499 1008 1585 588 538  IonicNO3 1377, 761 -OH2 3300, 821 10 2958 - 1533 1031 1587 577 510 -- 11 2951 -- 1541 1049 1558 592 416  IonicNO3 1384, 823 -OH2 3392, 877 12 2954 -- 1499 1012 1589 594 474 -- 13 2958 -- 1500 1022 1595 560 480 -- 14 2954 -- 1499 1022 1589 570 490  - ionic Cl -,648 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 322 | P a g e 3- 1HNMR spectra: The proton nuclear magnetic resonance spectrum for the L1 and L2 was carried out using DMSO-d6 as solvent and the following peaks were detected (Mohiuddina,2019) as shown in Table (6). Table (6 ) : 1 H.NMR data of ligands L 1 and L2 , DMSO-d6 ( ppm ) Chemical shift Functional groups L2 L1 0.82(d,6H) 0.85(d,6H) 0.81(d,6H) 0.85(d,6H) CH32 1.39(d,3H) 1.41(d,3H) 1.35(d,3H) 1.37(d,3H) CH3 1.75-1.83 (m,1H) 1.75-183 (m,1H) CH 2.20(s,3H) 2.27(s,3H) --- N=C-CH3 2.37(d,2H) 2.40(d,2H) 2.37(d,2H) 2.41(d,2H) CH2 3.98(q,1H) 4.70(q,1H) 3.64(q,1H) 4.57(q,1H) CH-CO --- 3.80(s,3H) 3.85(s,3H) OCH3 7.07-7.78 (m,9H) 6.77-7.28 (m,7H) Ar-H --- 7.77(s,1H) 8.07(s,1H) N=CH --- 9.47(s,1H) 9.53(s,1H) OH 10.47(s,1H) 11.10(s,1H) 11.34(s,1H) NH American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 323 | P a g e 4- X-ray Powder Diffraction Analysis The XRD patterns indicate a crystalline nature for metal complexes. Indexing of the diffraction patterns was performed using high Score Plus Software (Match program). For Co(II) and Cd(II) complexes, for example , their Miller indices (hkl) along with observed and calculated 2Ø angle , d values, and relative intensities , From the indexed data the unit cell parameters were also calculated and the powder XRD patterns of the compounds are completely different from those of the starting materials (Stou and. Jensen 1968), demonstrating the formation of coordination compounds. It is found that Co(II) and Cd(II) complexes have orthorhombic and tetragonal structure. Moreover , using diffraction data , the mean crystallite sizes of the complexes, D ,were determined according Scherrer equation (D = 0.9 λ / ( β cos θ ), where λ X -ray wavelength ( 1.5406 A-˚) , θ is Bragg diffraction angle, and β is the full width at half maximum of the diffraction peak ( Hong .. etal .,.2014) as shown in Table ( 7) . : Crystal data and structure refinement for complexes Table 7 No Complex 1 1 Molecular Formula CoC42H52N4O6Cl2 2 Molecular weight 838 3 Crystal system Orthorhombic 4 Space group P21 (42) 5 Unit cell parameters (Ao) a= 7.1692 Ao , b= 12.2813 Ao , c= 16.1892 Ao 6 Cell Volume (Ao3) 962.33 7 Z 8 8 θ range , deg 4.17 – 42.17 9 Index ranges 2  h  8, 0  k  12, 2  L  4 No Complex 7 1 Molecular Formula CdC42H52N4O6Cl2 2 Molecular weight 891 3 Crystal system Tetragonal 4 Space group P-4, 2,2 5 Unit cell parameters (Ao) a= 9.5142 Ao , b=9.5371 Ao, c= 8.2117 Ao 6 Cell Volume (Ao3) 1017.2 Ao 7 Z 4 8 θ range , deg 95.72 – 22.34 9 Index ranges 2  h 4 1  k  2 1  L  2 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 324 | P a g e CONCLUSION From the FT-IR data showed that ligands L1 and L2 act as bidentate coordinated to the metal ions through oxygen carbonyl and azomethine nitrogen atoms. Also the above discussion of various physicochemical, spectral and according to the measurements of XRD analysis, the crystal geometries of some complexes has been established, and we concluded that the metal ions are hexacoordinate with most probable octahedral structure has been suggested for most complexes. Whereas cadmium complexes have tetrahedral geometries. Fig.(1). Fig.(1): The structure of the prepared complexes American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 05, June, 2022 325 | P a g e References: 1. Abbas A.H. , Elias A.N. and Fadhil A.A. (2015) , "Synthesis, characterization and biological evaluation of new potentially active hydrazones of naproxen hydrazide.,"Der Phar.chem. , 7(10),93-101. 2. Al- Shaheen A. 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J. and AI-Shaheen A. 1., (1994), "Complexes of Hydrazide Schiff Bases", Transition, Met-Chern., 19,275. 30. Stout, C.H L.H. Jensen (1968), "X-ray Structure Determination", Macmillan, N.Y Fig (2): FT-IR Spectrum of (L1) Fig (3): FT-IR Spectrum of complex ( 10 )