American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 1 | P a g e INVESTIGATION OF SOME NON-STEROIDAL COMPLEXES 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 In this study we describe the synthesis and characterization of four and six coordinated compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with diclofenacyl hydrazide and vanillin or acetophenone ligands (L1andL2).These complexes were characterized by many physicochemical methods such as elemental analysis (CHN),magnetic susceptibility, molar conductance as well as spectral studies such as IR and UV-Visible , and X-ray powder diffraction measurementsT. The ligands have been investigated by NMR spectra,. Furthermore, the complexes have been found to have the formulaes : [M(L)2Cl2] where, M= Co(II) , Ni(II) , Cu(II) and Zn(II), whereas, the formula [M(L)2(H2O)2]X2 , M= Co(II) , Ni(II) , Cu(II) and Zn(II), X= NO3- , Cl- . [M(L)2]X2 , where, M= Ni(II) , Cu(II) and Cd(II), X= NO3- , Cl- . 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. On the basis of the above physicochemical measurements, the complexes have an octahedral and tetrahedral or square planar geometries. Keywords: X-ray powder diffraction, Metal complexes, diclofenacyl Complexes. 1. Introduction The first time in 1979, Alfred and Rudolf had prepared diclofenac which 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 [1,2]. Diclofenac is 2-(2,6-dichloranilino) phenyl acetic acid, In recent years it has become evident that dicloinhibicyclooxygenase 1 and 2 which are the enzyme responsible forproducing prostaglandins contribute to inflammation from a varity of causes[3] .This led to the introduction of new compounds with an improved profile our aim to develop new safer drugs and improving the pharmacokinetic and pharmacotoxicological profile through complexation [4 ]. 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[5 ] is useful in sepsis-induced acute American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 2 | P a g e pneumonia, 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, acetophenone ) show the importance of hydrazone complexes in various fields including analytical and biological field [6].Hydrazone derivatives possessing anti-inflammatory, analgesic, antipyretic and antibacterial activities are also reported in the literature[ 7]. These complexes which plays an important role in reducing the toxicity of the parent drug and acts as apro-drug [ 8&9 ]. 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- SMPIO melting point apparatus . .IR spectra measurements were recorded using FTIR-Tensor 27-Burker Co.Germany 2003, as kBr pellets in the range in the range (400-4000 cm-1). UV-Visible spectral measurements were recorded using Shimaduz 160 spectrophotomer for 10-3 M complexes in DMF solvent at room temp.using 1cm quarts cell in range (200-900)nm . Elemental analysis were carried out on a CHN analyzer type Vector, model EA 3000 single V.3.0 single Euro . The NMR was recorded on Agilant Varian (USA), 500 MHz using deutrated DMSO-d6 as a solvent. Molar conductance of complexes were measured at room temp for 10-3 M in DMF using (BC 3020 professional Bench top conductivity) Magnetic susceptibility of the complexes was carried out by (Magnetic Susceptibility Balance of Johnson Mattey catalytic system division , (England) .Via Faradys method at room temperature. Metal contents were estimated spectrophotometrically using atomic absorption spectrometer NOVAA 350 Scientific Equipments. X-ray powder diffraction data for compounds were measured by using x-rd xpert PA analytical Phillips Holland and the crystal data for compounds were analyzed by using match program version 1.6 C. Preparation of the Ligands and the Complexes 1. Synthesis of 2-[(2,6-dichloro-anilino)phenyl acetic acid This carboxylic acid was prepared by dissolving (15.9 g,0.05 mole) of sodium diclofenac in 45ml of absolute ethanol and then to that drops of conc. hydrochloric acid was added until white precipitated was formed, filtered and washed with cold distilled water and cold absolute ethanol and dried in vacuum many hrs. as in Scheme 1. The yield (85%), b.p 153-155 oc , empirical formula C14H11NO2Cl2 , White ppt. American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 3 | P a g e %N %H %C 4.72 3.71 56.75 Calc. 4.81 3.62 57.00 Found 2. Synthesis of 2-[(2,6-dichloro-anilino) phenyl acetic acid ethyl ester The carboxylic acid which was prepared in previous step was esterified by dissolving( 11.84 g, 0.04 mole) of it in 35ml of absol.ethanol in presence of 2.0ml of sulfuric acid. The mixture was refluxed for 8hrs . 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 , (Scheme 1). The yield (72%) , b.p 75- 77 oc ,empirical formula C16H15NO2Cl2 ,orange ppt. %N %H %C 4.32 4.62 59.52 Calc. -4.52 4.70 59.49 Found 3. Synthesis of 2-[(2,6-dichloro-anilino)phenyl acetic acid hydrazide The hydrazide was prepared [4] by refluxing (9.72g , 0.03mol) of 2-[(2,6-dichloro- anilino)phenyl acetic acid ethyl ester in 30ml absol.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 and dried in an oven at (70-80) C , (Scheme 1). The yield (80%), mp 136-134C, empirical formula C14H13 N3 OCl2., white ppt. %N %H %C 13.54 4.19 54.19 Calc. 13.55 4.30 54.23 Found 4.Synthesis of hydrazone ligands (L1 & L2) The ligands synthesized according to the method described in the literature [10] by reacting equimolar amount of diclofenacyl hydrazide and vanillin or acetophenone .A hot ethanolic solution of the ligand made by dissolving ( 3.1g, 0.01 mole) of diclofenacyl 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 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 4 | P a g e from ethanol, washed with ether and dried under vacuum. The structures of the ligands are shown in Scheme 1. 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 C22H19 N3 O3Cl2 444 white 103-104 %71 59.45 (59.73) 4.27 (4.40) 9.45 (9.55) L2 C22H19 N3OCl2 412 white 108-110 %79 64.07 (64.24) 4.61 (4.73) 10.19 (10.03) 4.Synthesis of the complexes The complexes were obtained by adding an ethanolic solution of metal(II) chloride or nitrate (0.005mol) with the ligand L1(4.44 gm , 0.01mol) or L2 (4.12gm , 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 06, July, 2022 5 | 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 [11]. Table 2 : Weight of metal salts used to prepare complexes . Table 3 : Characterization , analytical , molar conductance and magnetic susceptibility data of the complexes . 5.Results and Discussion Molar conductance values of complexes(1, 6,8,9,10 and 13) in 10-3 M DMF are neutral .while complexes (2,3,4,5,7, 11,12and 14) are 1:2 electrolytic nature for nitrate or chloride complexes. The molar conductance values and the metal contents are in a good agreement with given formulations [12],(Table 3). 1-Electronic Spectra and magnetic moment Measurements: 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 ZnCl2 0.68 NiCl2. 6H2O 1.18 CdCl2 0.91 Ni(NO3)2.6H2O 1.45 NO . Formula Molecula r Weight Colour Yield m.p (C)º Meff B.M ΛM DM F Cm2 .Oh m- 1.m ol- Calculate( Found )% %C %H %N %M 1 [Co(L1)2Cl2] 1018 Brown 69 >300 4.76 15 51.86 (52.03) 3.73 (3.60) 8.25 (8.48) 5.79 (6.01) 2 [Co(L1)2(H2O)2](NO3) 2 1109 Brown 69 >300 4.67 107 47.61 (47.92) 3.78 ( 4.00) 10.09 (10.13) 5.32 (6.01) 3 [Ni(L1)2]Cl2 1017.7 Orange 76 297 Dia 129 51.88 (52.00) 3.73 (3.92) 825 (817) 5.76 (5.87) 4 [Ni(L1)2 (](NO3)2 1070.7 Orange 74 >300 Dia 111 4931 (49.50) 3.54 (3.62) 7.84 (7.96) 5.48 (5.52) 5 [Cu(L1)2] Cl2 1022 Green 64 >300 1.82 119 51.66 (51.88) 3.71 (3.96) 8. 21 (8.03) 6.16 (6.00) 6 [Zn(L1)2Cl2] 1024 Yellow 78 >300 Dia 22 51.56 (51.93 3.71 (3.99) 8.20 ( 8.02) 6.34 (6.55) 7 [Cd(L1) ]Cl2 1071 Yellow 72 >300 Dia 126 49.29 (49.18) 3.54 (3.61) 7.84 (7.96) 10.45 (10.66) 8 [Co(L2)2Cl2] 954 Brown 68 >300 4.79 18 55.344 (55.00) 3.98 (4.03) 8.80 ( 9.19) 6.18 (6.27) 9 [Co(L2)2 (NO3)2 ] 1007 Brown 67 >300 4.75 27 52.43 (52.61) 3.77 (4.03) 11.12 (119)9 5.85 (6.00) 10 [Ni(L2)2Cl2] 953.7 Green 71 >300 3.31 14 55.36 (55.49. 3.98 (4..01) 8.80 (9.02) 6.15 (6.00) 11 [Ni(L2)2(H2O)2](NO3)2 989.7 Green 64 >300 2.92 137 50.63 ( 50.51) 4.02 (4.15) 8.05 ( 8.12) 6.58 (7.00) 12 [Cu(L2) 2(H2O)2 ] ] Cl2 994 Green 79 >300 2.01 129 53.11 (53.00) 4.20 (4.41) 8.45 (8.57.) 6..33 6..50) 13 [Zn(L2)2 (H2O) 2]Cl2 996 Yellow 74 >300 Dia 14 53.01 (53.09) 4..21 (4.32) 8.43 (8.56) 6.52 (6.69) 14 [Cd(L2)2] Cl2 1043 Yellow 74 >300 Dia 125 51.06 (49.89) 3.64 (3.70) 8.05 (7..88) 10.73 (10.98) American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 6 | P a g e The ultraviolet spectra of the two ligands L1 and L2 and their complexes in DMF solution have been recorded giving ultraviolet spectra, d-d spectra and charge transfer spectra (Table 4 ), and these ligands exhibited two bands at (31746,33557) cm-1, (25062,29069) 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 shifited to lower frequencies confirming the coordination of the ligands to the metal ions [13] and these values agree with the magnetic moments obtained for hexacoordinated cobalt(II) complexes 1,2,8, and 9 and this value greater than theoretical value (3.87) B.M. due to orbital [14,15]The electronic spectra of these Co(II) complexes exhibited three bands due to ν1 at (11261-13480) cm-1 , ν2 at (14749-16482) cm-1 and ν3 at(16177-21929) 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. For the hexacoordinated Ni(II) complexes 10,11 exhibit electronic spectrum bands at (12814 , 13333)cm-1 , (16286 , 17815) cm-1 and (22367 , 26041) 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 complex is confirmed by the measured magnetic moment values (2.89 , 3.28)B.M.[15,16]. While tetracoordinated Ni(II) complexes 3&4 exhibited two bands due to two 1A1g 1A2g 1A1g 1B2g transitions ν1 at (20533,16694 ) cm-1 , ν2 at (28818,29239) cm-1 and charge transfer at( 35715 and 36231 cm-1 respectively and is confirmed with the measured diamagnetic moment values and is agree with square planar configuration. While the Cu(II) complex 5 exhibits a broad electronic band due to transition 1A2g (F) 1A2g (F) at (9000-12000) cm-1and is confirmed with the measured magnetic moment value 1.82 B.M. and is agree with square planar configuration. The octahedral Cu(II) complex 12 showed one band at (18456) cm-1 and this band may arise from the 2Eg 2E1g transition , the magnetic moment obtained for this complexe is confirmed with the measured magnetic moment values (2.01 B.M) [17] (Table 4). is agree with octahedral geometry. American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 7 | P a g e Table 4 : Electronic spectra data of the complexes CT = Charg transfer band 2-Infrared Spectra The free ligands L1 and L2) showed IR spectra bands at 2950 and 2924cm-1which are characteristic of stretching vibration[18]of the NH and other absorption band appeared at (1639 and 1662)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 ion [19]. Also showed a strong band in the region (1506 and 1548)cm-1 , which is characteristic of the azomethine (stretching vibration of (C=N) group and is shifted to lower frequency indicating coordination of azomethine nitrogen atom to the metal[20]. 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 [21] The aqua complexes contain weak to medium abroad band at (3200 – 3600) 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 [22,23]. 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[24]. 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 showed a band at(545- 765)cm-1 has been attributed to ionic chloride [21].On the other hand, the spectra of some complexes showed the presence of a band at (1380-1392) cm-1 due to ionic nature of nitrato group[19] (Table 5). Comp.No. Electronic transition of d-d cm-1 CT ν1 ν 2 ν3 1 11261 16482 21929 38167 2 13480 14749 20618 33898 3 20533 28818 - 35715 4 16694 29239 - 36231 5 14513 - - 29239 8 13333 16306 20491 38464 9 12738 14970 16177 33222 10 13333 16286 22367 31446 11 12814 17825 26041 37313 12 18456 - - 36101 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 8 | P a g e Table 5: Selected I.R. bands of the ligands and its complexes (in cm-1) 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 [5]as shown in Table(6). Comp No.  (N-H)  (O-H)  (C=N)  (N-N)  (C=O)  (M-O)  (M-N) Other L1 2956 3200- 3300 1589 1076 1661 -- -- -- L2 2956 - 1595 1060 1620 -- -- -- 1 2950 3200- 3300 1452 1026 1583 507 440 -- 2 2952 3200- 3600 1452 1026 1577 605 450  IonicNO3 1380, 827 -OH2 3600, 765 3 2956 3200- 3600 1452 1029 1583 665 450  - ionic Cl - ,605 4 2956 3200- 3600 1450 1022 1585 607 460  IonicNO3 1380, 8251 5 2956 3200- 3300 1452 1028 1581 609 465  - ionic Cl - ,550 6 2952 3200 - 3600 1450 1026 1589 610 437 -- 7 2950 3200- 3600 1450 1031 1591 617 435  - ionic Cl 570 8 2954 -- 1534 1028 1643 612 428 -- 9 2956 -- 1539 1007 1643 603 400  N-O ,950, as No2-,1295 s- No2-1400 10 2954 - 1502 1000 1649 628 400 -- 11 2954 -- 1571 1025 1641 550 418  IonicNO3 1392, 825 -OH2 3200, 760 12 2956 -- 1471 1055 1638 553 420  - ionic Cl 560 -OH2 3200, 761 13 2954 -- 1539 1058 1639 565 424  - ionic Cl - ,509 ,,-OH2 3200, 765 14 2954 -- 1539 1055 1639 575 445  - ionic Cl - ,545 American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 9 | P a g e Table (6 ) : 1 H.NMR data of ligands L1 and L2 in DMSO-d6 Chemical shift (ppm) Effective functional groups L2 L1 2.30(s,3H) 2.35(s,3H) --- N=C-CH3 3.86(s,2H) 4.18(s,2H) 3.69(s,2H) 4.13(s,2H) CH2-CO --- 3.80(s,3H) 3.84(s,3H) OCH3 6.28-7.87 (m,12H) 6.28-7.55 (m,10H) Ar-H --- 7.77(s,1H) 7.95(s,1H) N=CH 8.17(s,1H) 8.12(s,1H) 8.15(s,1H) NH --- 9.53(s,1H) 9.56(s,1H) OH 10.77(s,1H) 10.89(s,1H) 11.49(s,1H) 11.65(s,1H) NH-CO 4- X-ray Powder Diffraction Analysis The diffraction patterns for metal complexes was performed using high Score Plus Software (Match program). , the Miller indices (hkl) along with observed and calculated 2Ø angle , d values, and relative intensities the unit cell indexed data parameters were also calculated and the powder XRD patterns of the compounds are completely different from those of the starting materials, 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 [26,27] Hong .. etal .,.2014) as shown in Table( 7) . American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 10 | P a g e Crystal data and structure refinement for complexes Table 7 No Complex 1 1 Molecular Formula CoC44H38N6O6C6 2 Molecular weight 1018 3 Crystal system Monoclinic 4 Space group P10 (43) 5 Unit cell parameters (Ao) a= 6.2319 Ao , b= 12.7319 Ao , c= 16.1098 Ao 6 Cell Volume (Ao3) 963.33 7 Z 8 8 θ range , deg 2.47 – 29.69 9 Index ranges 2  h  6, 0  k  12, 2  L  2 No Complex 12 1 Molecular Formula CuC44H42N6O4Cl6 2 Molecular weight 994 3 Crystal system Orthorhobic 4 Space group P.21(40) 5 Unit cell parameters (Ao) a= 12.0197 Ao , b=11.9372 Ao, c= 6.0482 Ao 6 Cell Volume (Ao3) 1012.3 Ao 7 Z 8 8 θ range , deg 20.7 – 28.2 9 Index ranges  h 1 0 1  k  2 1  L  2 5. Conclusion 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 from the ir data the ligands L1 and L2 act's as bidentate coordinated to the metal ions through oxygen carbonyl and azomethine nitrogen atoms. Whereas the metal ions are hexacoordinate with most probable octahedral structure or tetracoordinate with square planar or tetrahedral structure have been suggested for most complexes. Fig.(1). American Journal of Interdisciplinary Research and Development ISSN Online: 2771-8948 Website: www.ajird.journalspark.org Volume 06, July, 2022 11 | P a g e 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 06, July, 2022 12 | P a g e References 1. 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