        Transition metal complexes of new legend 2,2'-[(1E,2E)-ethane-1,2-diylidenedi(2E) hydrazin-1-yl-2-ylidene] bis (5-methyl-1,3,4-oxadiazole) with some transition metal ion such as Cr3, Co3+, Ni2+  were synthesis ,characterization by magnetic susceptibility measurements, conductance, elemental analyses, 1HNMR, IR, and mass  spectra. The electrolytic behavior were confirmed from their conductance. data spectral study of transition metal complexes suggest octahedral geometry for  Cr3+, Co3+ ion , square planer geometry for Ni2+.The effective magnetic moment of cobalt complex is 0.91 that mean the Co2+ oxidation to Co3+. The complexes and ligand were tested against two types of bacteria (Staphylococcus aureus, Escherichia coli) all prepared complexes showed good biological activity.



Azhar  H. Katea

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University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  69      Synthesis , Characterization , Antimicrobial  New 2,2'-[(1E,2E)-ethane-1,2-diylidenedi(2E)hydrazin-1-yl-2-ylidene]bis (5-methyl-1,3,4-oxadiazole) and their transition metal complexes   *Azhar H. Katea        Saher A. Ali           Ibrahim A. Flifel  Department of chemistry- College of science - University of Thi-qar  *E-mail: azharh332@gmail.com  Abstract         Transition metal complexes of new legend 2,2'-[(1E,2E)-ethane-1,2-diylidenedi(2E) hydrazin-1-yl-2-ylidene] bis (5-methyl-1,3,4-oxadiazole) with some transition metal ion such as Cr3, Co3+, Ni2+  were synthesis ,characterization by magnetic susceptibility measurements, conductance, elemental analyses, 1HNMR, IR, and mass  spectra. The electrolytic behavior were confirmed from their conductance. data spectral study of transition metal complexes suggest octahedral geometry for  Cr3+, Co3+ ion , square planer geometry for Ni2+.The effective magnetic moment of cobalt complex is 0.91 that mean the Co2+ oxidation to Co3+. The complexes and ligand were tested against two types of bacteria (Staphylococcus aureus, Escherichia coli) all prepared complexes showed good biological activity. Keywords: - Oxadiazole, Transitions metal complexes, biological activity.    الخالصة-1E,2E)-ethane-1,2-diylidenedi(2E) hydrazin-1-yl-2-ylidene]bis(5-methyl-1,3,4)]-'2,2حضر الميكاند الجديد         oxadiazole)  مع بعض العناصر االنتقالية مثلCr3, Co3+, Ni2+  وشخصت باستخدام قياسات الحساسية المغناطيسية وقياسات التوصيمية والتحميل الدقيق( وطيف الكتمة . ومن النتائج التي H1NMR(  وطيف البروتون النووي المغناطيسي )IR( وتقنيات أخرى منها طيف االشعة تحت الحمراء )CHNلمعناصر ). العزم المغناطيسي الفعال لمعقد الكوبمت بين +Ni2 والشكل المربع المستوي لمعقد   +Cr3, Co3تم الحصول عميها اقترح الشكل الثماني السطوح لمعقد  (Staphylococcus aureus, Escherichia coli) . اختبار الفعالية البيولوجية لميكاند ومعقداته ضد نوعين من البكتريا   +Co3 الى +Co2تأكسد  أعطت نتائج جيدة .         1. Introduction         1, 3, 4 -oxadiazole is classify as heterocyclic aromatic chemical compound of University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  69  the azole family; with the molecular formula C2H2N2O . The1,3.4- oxadiazole exist in different isomeric forms such as 1,2,4- oxadiazole, 1,2,5- oxadiazole, 1,2,3- oxadiazole and 1,3,4-oxadiazole(Kumar et al. 2012) . The 1,3,4- oxadiazole heterocyclic compound which has been commonly used as a privileged scaffold to produce various novel pharmaceutical drug  such as : Antimicrobial(Prakash et al. 2009) P, Antifungal(Frank & Kalluraya 2005),  anticancer (Rao & Anto 2013), P Antihypertensive(ILANGOVAN et al. 2015) , Anti-inflammatory(Burbuliene et al. 2004) and Anticonvulsant(Akbarzadeh et al. 2003) .  This class of material also has gained the worth of modern application such as Insecticidal (Kolli 2016), Antioxidant (Kuş et al. 2008) , Dyes (Hunger 2003) and Polymers  (de Oliveira et al. 2012) (de Oliveira, Lira, Barbosa-Filho, Lorenzo, & de Athayde-Filho, 2012) materials[11]  .1,3,4-oxadiazole derivatives are as well used as employed electron conducting and hole blocking  materials in organic light-emitting diodes(LEDS)[12], Also use in the extraction of transition metal complexes .  2. Experimental 2.1.  Synthesis of the ligand:       New ligand 2, 2'-[(1E, 2E)-ethane-1, 2-diylidenedi (2E) hydrazin-1-yl-2-ylidene] bis (5-methy l-1,3,4-oxadiazole) (Scheme 1) was prepared as follows:-   ethyl acetate (0.1mol,10.5ml) was added to hydrazine monohydrate (0.15mol,7.5ml) in ethanol absolute (100ml). The resulting mixture was heated under reflux for (6hours). The mixture was concentrated, The product was filtered and washed with ethanol to give the product (A) Acetic acid hydrazide (liquid) , colorless ,boiling point 129 °C, yield 90% ) (Manjunath et al. 2015).       Acetic acid hydrazide (A) (0.1mol, 10ml) mix with (0.1mol, 5.6g)of Potassium Hydroxide dissolved in(100 ml) absolute ethanol then added carbon disulfide (0.1mol,6ml). The resulting mixture was mixing by shaking and heated at (80) °C under reflux for (20hours). The resultant was concentrated, and carefully acidified with hydrochloric acid HCl (5%) to give yellow precipitate. The product was filtered and washed with cold water and ethanol to give the desired product 5-methyl-1,3,4-oxadiazole-2-thiol (B) (solid, yellow, melting point 188 °C, yield %89)(Khiati et al. 2007)(Hayal 2014). 5-methyl-1,3,4-oxadiazole-2-thiol (B)(0.1mol, 11.6g) was mixed with access of hydrazine (0.1mol,4ml) dissolved in (50ml) ethanol and refluxed to (10hours) then allowed to cool, the yellow precipitate of 2-hydrazinyl-5-methyl-1,3,4-oxadiazole(C) was filtered off and recrystallized from ethanol (solid, pale yellow, melting point 222°C, yield 90%) (Moustafa et al. 2002). The Schiff bases have been synthesized by condensation of 2-hydrazinyl-5-methyl-1, 3, 4-oxadiazole(C) and glyoxal in 2:1 molar proportions in ethanol absolute (100ml) for (3hours). The brown precipitate of ligand formed were filtered, washed with cold ethanol absolute and recrystallized from hot ethanol absolute(solid, brown, melting point 197°C, yield 80%) (Hanif & Chohan 2013). scheme1      2.2.   Preparation of complexes       A solution of CoCl2.6H2O, CrCl3.6H2O and NiCl2.6H2O) (0.001 mol) was mixed with (L) (0.001 mol) in ethanol absolute and refluxed for 2 hrs. the precipitated complex was filtered, washed with ethanol absolute.  Scheme 1. Synthesis of ligand ( L) University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  66  2.3. Measurements           Elemental microanalysis CHN were carried out on a Thermofinigan flash analyzer, the FTIR spectra in the range (200-4000) cm-1 were recorded as CsI discs using a Shimadzu FTIR spectrophotometer, molar conductance measurements were made in anhydrous DMSO at 25 oC using Inolabcond 720.The 1H NMR spectra were recorded on a Mercury-300BB NMR 300 spectrometer, relative to the internal standard tetramethylsilane (TMS), DOSO-d6 used as solvent. Melting points were determined in open capillary tubes using an electro thermal melting point /SMP3 apparatus. Mass spectra were recorded in the range (0-800) m/e on a 5973 network mass selective detector. Balance Magnetic susceptibility were recorded inModel MSB-MKI.  3. Results & Discussion       The physical properties of ligand and its complexes are presented in table 1. Elemental microanalysis CHN shown in table 2.             3.1.   Infra-Red Spectroscopy            Infrared spectroscopy is one of the most commonly used tools for the detection of functional groups in pure compounds and complexes. The spectra for L shows a characteristic stretching absorption bands at (3452, 3421, 2934, 1523, 1627, 1475,1365, 1025,) cm-1  assigned to υ(N-H) ,ʋ(N–H) , ʋ(N–H) , ʋ(C=N), ʋ(C=N) (Field et al. 2012), symmetrical and Asymmetrical C-O-C stretching respectively(Huang et al. 2003) . The C=N and C-O-C are important to predict the bonding mode of the ligand ,these bands  shift higher wavenumber in the spectra of complexes compare with ligand, observed changes are the evidences of complexation had happened . The IR data of the ligand and complexes are shown in Table (3) and figure (8),(9) and(10) . The Table lists the stretching frequency (υ) for some of the characteristics groups exhibited by the ligand and complexes.   3.2.  Nuclear Magnetic Resonance         The H1 NMR spectral data for the 2,2'-[(1E,2E)-ethane-1,2-diylidenedi(2E)hydrazin-1-yl-2-ylidene]bis(5-methyl-1,3,4-oxadiazole)  gave additional support for the suggested structure of the ligand. The spectra exhibit a triplet at (2.6ppm,6H) due to two methyl group (Laskar et al. 2016), singlet peaks exhibit at (6.1 ppm, 2H) due to NH group (Singh et al. 2012), another singlet peaks observed at(9.3ppm,2H) due to CH=N(Rezki et al. 2015) .The H1NMR of ligand shown in figure (11).  Mass spectra   3.3.         The mass spectra of the ligand and its transition metal complex were recorded at room temperature ,The mass spectrum of the ligand shows a molecular ion peak [M0] at m/z =250 . The fragmentation pathways of ligand give the peaks at different mass numbers at m/z = (218,167, 136, 125, 98 and 83)due to [C8H10N8]+., [C5H7N6O]+., [C4H4N6]+., [C4H5N4O]+., [C3H4N3O]+., [C3H3N2O]+. Respectively. The intensity of these peaks reflects the stability and abundance of the ions . as shown in Figure (12-17) and (Scheme 2). The complex [Cr(L) Cl2]Cl showed a molecular ion peak at m/z [M0]= (659) which is equivalent to molecular mass of the complex. This complex shows another a fragmentation peak with loss of chlorine atom at Table 1. conductance, physical properties data of the ligand and its complexes . Table 2. Elemental microanalysis CHN for the ligand . Table 3 . Characteristic absorption bands of ligand and its complexes . University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  000  m/z(623).the complex spectrum shows fragment ion peak with loss two chlorine atom at m/z (588, 552) due to[Cr(L)2Cl] +.and [Cr(L)2] +. respectively .  The mass spectrum of the complex [Co (L) Cl2] shows a molecular ion peak at m/z [M0] (380) which is equivalent to molecular mass of the complex. This complex spectrum shows fragment ion peak with loss chlorine atom at m/z (345, 309) due to [Co (L) Cl]+. and [Co (L)2]+. respectively. The mass spectrum of the complex [Ni(L)Cl2] shows a molecular ion peak at m/z [M0]( 380), This complex shows another a fragment ion peak with loss of chlorine atom at m/z (345)and (309). the mass spectra of the complexes shown in figure(12), (13),(14),(15) .   3.4. Magnetic susptibility         The value of the effective magnetic moment of the complexes is tabulated in table 1 by using Balance Magnetic susceptibility. The Results are shown in the table above all the complexes given low value of effective magnetic moment. Chromium ion Cr3+ shows the highest value (4.28) M.B due to the presence of three single electrons compare the low value (0.91) M.B for Co3+ ion and (0.42) M.B for nickel ion Ni2+ because there is no single electron for cobalt ion Co3+ and nickel ion Ni2+ . We conclude that the ligand works as strong ligand (strong field).                                  Figure 1 . Graphical presentation of stereochemistry of the Ligand (C16H14N4SO)  Electrostatic potential 2D  for Ligand   Figure 2 .  Figure 3 . Graphical presentation of stereochemistry of the [Cr(L)2Cl2]Cl  Figure 4 . Graphical presentation of stereochemistry of the [Ni(L1)Cl2]  Figure 5 . Graphical presentation of stereochemistry of the [Co(L1)Cl2]  University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  000                   Analytical and spectral data (1H NMR, IR, mass spectra ) of all synthesized compounds were in full agreement with the proposed structure.  3.5. Biological Study         The ligand and its transition metal complexes were evaluated for antimicrobial activity against gram positive bacteria such as Staphylococcus aureus and gram negative bacteria Escherichia coli, by using agar well diffusion method. All the microbial cultures were adjusted to 0.5 McFarland standard, dimethyl sulphoxide (DMSO) were used to prepared all the test solution. The area of inhibition was measured in millimeter. nutrient agar used as culture medium (Balouiri et al. 2016) , the values of the investigated compounds are tabulated in Table.4.The observe result showed transition metal complexes enhanced antimicrobial activity than that of free ligand. This result can be due to the greater lipophilic nature of the complexes and favors its permeation through the lipoid layers of the bacterial membranes. The activity of transition metal complexes can be expound  on the basis of Overton’s concept  and Chelation theory (Chen et al. 2007).    4. Conclusion         The ligand 2, 2'-[(1E, 2E) -ethane-1,2-diylidenedi(2E)hydrazin-1-yl-2-ylidene]bis(5-methyl-1,3,4-oxadiazole) was successfully synthesized. Elemental microanalysis CHN, IR, 1H NMR and mass spectral observations suggest the octahedral geometry for the Cr(III), Co(III). Square planar geometry was proposed for Ni(II) .  Figure 6 . [Cr(L)2Cl2]Cl  Figure 8 . [Ni(L1)Cl2]  Figure 7 . [Co(L1)Cl2]  Table 4 . Antibacterial screening data of the ligand and its metal complexes Figure 9 . Antibacterial of the ligand and its metal complexes  University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  001                      Scheme 2. Suggested mass fragmentation of ligand.  Figure 10 . IR spectra of Ligand (C8H10N8O2)  Figure 11 . IR spectra of [Cr(L)2Cl2]Cl Figure 12 . IR spectra of [Co(L)Cl2]  Figure 13 . IR spectra of [Ni(L)Cl2] Figure 14 . NMR spectra of the ligand (C8H10N8O2) University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  002                     References  Akbarzadeh, T. et al., 2003. Design and synthesis of 4H-3-(2-phenoxy)phenyl-1,2,4-triazole derivatives as benzodiazepine receptor agonists. Bioorganic and Medicinal Chemistry, 11(5), pp.769–773. Balouiri, M., Sadiki, M. & Ibnsouda, S.K., 2016. Methods for in vitro evaluating antimicrobial activity: A review. Journal of Pharmaceutical Analysis, 6(2), pp.71–79. Available at: http://dx.doi.org/10.1016/j.jpha.2015.11.005. Burbuliene, M.M. et al., 2004. Synthesis and anti-inflammatory activity of derivatives of 5-[(2-disubstitutedamino-6-methyl-pyrimidin-4-yl)-sulfanylmethyl]-3H-1,3,4-oxadiazole-2-thiones. Il Farmaco, 59(10), pp.767–774. Available at: http://linkinghub.elsevier.com/retrieve/pii/S0014827X04001466. Chen, C.J. et al., 2007. Synthesis and antifungal activities of 5-(3,4,5-trimethoxyphenyl)-2-sulfonyl-1,3,4-thiadiazole and 5-(3,4,5-trimethoxyphenyl)-2-sulfonyl-1,3,4-oxadiazole derivatives. Bioorganic and Medicinal Chemistry, 15(12), pp.3981–3989. De Oliveira, C.S. et al., 2012. Synthetic approaches and pharmacological activity of 1, 3, 4-oxadiazoles: a review of the literature from 2000--2012. Molecules, 17(9), pp.10192–10231.  Field, L.D., Sternhell, S. & Kalman, J.R., 2012. Organic structures from spectra, John Wiley & Sons. Frank, P. V & Kalluraya, B., 2005. Synthesis of 1 , 3 , (C8H10N8O2) mass spectra of ligand Figure 15 .   Figure 16 . mass spectra  of [Cr( L)2Cl2]Cl Figure 17 . mass spectra  of [Co(L)Cl2]  [Ni(L)Cl2] Figure 18 .  mass spectra of  University of Thi-Qar Journal Of Science (UTsci) Website: http://jsci.utq.edu.iq                                                                       Email: utjsci@utq.edu.iq Volume 6, Number 2, June 2017  003  4-oxadiazoles carrying imidazole moiety. , 44(July), pp.1456–1459. Hanif, M. & Chohan, Z.H., 2013. Synthesis, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases. Applied Organometallic Chemistry, 27(1), pp.36–44. Hayal, M.Y., 2014. Syntheses , Characterization and Antimicrobial Studies of a New Complexes with Some Transition Metal. , 9(1), pp.1–10. Huang, Q., Liu, C. & Song, G., 2003. Syntheses and insecticidal activities of novel 2 , 5-disubstituted. , 123, pp.163–169. Hunger, K., 2003. Industrial Dyes: Chemistry, Properties, Applications Edited by Klaus Hunger (Kelkheim, Germany). Wiley-VCH: Weinheim. 2003. xxiv + 600 pp. $185.00. ISBN 3-527-30426-6., Available at: http://pubs.acs.org/doi/abs/10.1021/ja0335418. ILANGOVAN, A., SARAVANAKUMAR, S. & UMESH, S., 2015. T3P as an efficient cyclodehydration reagent for the one-pot synthesis of 2-amino-1,3,4-oxadiazoles. Journal of Chemical Sciences, 127(5), pp.797–801. Available at: http://link.springer.com/10.1007/s12039-015-0834-x. Khiati, Z., Othman, A.A. & Guessas, B., 2007. Synthesis and Antibacterial Activity of 1 , 3 , 4-Oxadiazole and 1 , 2 , 4-Triazole Derivatives of Salicylic Acid and its Synthetic Intermediates. , pp.20–24. Kolli, S.K., 2016. SYNTHESIS , CHARACTERIZATION AND BIOLOGICAL ACTIVITY OF SOME NEW OF NOVEL 1 , 3 , 4-OXADIAZOLE BEARNING THIOPHEN-2-CARBOXYLIC ACID. , 5(5), pp.1800–1825. Kumar, K.A., Jayaroopa, P. & Kumar, G.V., 2012. Comprehensive Review On The Chemistry Of 1 , 3 , 4- Oxadiazoles And Their Applications. , 4(4), pp.1782–1791. Kuş, C. et al., 2008. Synthesis and antioxidant properties of novel N-methyl-1,3,4-thiadiazol-2-amine and 4-methyl-2H-1,2,4-triazole-3(4H)-thione derivatives of benzimidazole class. Bioorganic and Medicinal Chemistry, 16(8), pp.4294–4303. Laskar, K. et al., 2016. Synthesis, characterization and interaction studies of 1,3,4-oxadiazole derivatives of fatty acid with human serum albumin (HSA): A combined multi-spectroscopic and molecular docking study. European Journal of Medicinal Chemistry, 122, pp.72–78. Available at: http://linkinghub.elsevier.com/retrieve/pii/S0223523416304895. Manjunath, G. et al., 2015. Synthesis of new 5-((2-(substituted phenoxymethyl)-1H-benzo[d]imidazol-1-yl)methyl)-1,3,4-oxadiazole-2-thiol: A novel class of potential antibacterial and antifungal agents. Annales Pharmaceutiques Françaises, 73(6), pp.452–460. Available at: http://linkinghub.elsevier.com/retrieve/pii/S0003450915000577. Moustafa, O.S., Badr, M.Z.A. & El-Emary, T.I., 2002. New fused quinoxalines: Synthesis and reactions of pyrimidothienoquinoxaline and oxadizolylthienoquinoxalines. Bulletin of the Korean Chemical Society, 23(4), pp.567–570. Prakash, O. et al., 2009. Synthesis and antibacterial activity of 1 , 3-diaryl-4-cyanopyrazoles. , 48(April), pp.563–568. Rao, M.S.R.M.B.R. & Anto, R.J., 2013. CHEMISTRY Synthesis of piperazinyl benzothiazole / benzoxazole derivatives coupled with 1 , 3 , 4-oxadiazole-2-thiol : novel hybrid heterocycles as anticancer agents. , 3. Rezki, N. et al., 2015. Synthesis of novel 2,5-disubstituted-1,3,4-thiadiazoles clubbed 1,2,4-Triazole, 1,3,4-Thiadiazole, 1,3,4-Oxadiazole and/or schiff base as potential antimicrobial and antiproliferative agents. Molecules, 20(9), pp.16048–16067. Singh, A.K., Pandey, O.P. & Sengupta, S.K., 2012. Synthesis, spectroscopic and antimicrobial studies of zinc (II) derivatives with Schiff bases derived from 2-hydrazino-5-[substituted phenyl]-1, 3, 4-oxadiazole. Main Group Chemistry, 11(3), pp.175–187.    

Synthesis , Characterization , Antimicrobial  New 2,2'-[(1E,2E)-ethane-1,2-diylidenedi(2E)hydrazin-1-yl-2-ylidene]bis (5-methyl-1,3,4-oxadiazole) and their transition metal complexes

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Synthesis , Characterization , Antimicrobial New 2,2'-[(1E,2E)-ethane-1,2-diylidenedi(2E)hydrazin-1-yl-2-ylidene]bis (5-methyl-1,3,4-oxadiazole) and their transition metal complexes

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