SYNTHESIS AND MAGNETIC PROPERTIES OF 4H9 4 (ox)3
Indo. J. Chem., 2012, 12 (1), 89 - 9389SYNTHESIS AND MAGNETIC PROPERTIES OFBINUCLEAR COMPLEX [N(n-C4H9)4][MnIIFeIII(ox)3]Fahimah Martak*, Hamzah Fansuri, and Sekarayu Dianing PutriDepartment of Chemistry, Institut Teknologi Sepuluh Nopember,Kampus ITS Sukolilo Surabaya 60111Received September 7, 2011; Accepted February 10, 2012ABSTRACTIIIIIBinuclear complex, [N(n-C4H9)4][Mn Fe (ox)3] (ox oxalate), has been synthesized and characterized. BinuclearIIIIIcomplex with formula of [N(n-C4H9)4][Mn Fe (ox)3] was synthesized by forming precursor K3[Fe(ox)3] which wasfollowed by adding manganese chloride and tetrabutyl ammonium chloride. Characterization of the complex wasmade by microanalysis, FT-IR spectroscopy, x-ray diffraction and Magnetic Susceptibility Balance. MagneticIIIIImoment of binuclear complex [N(n-C4H9)4][Mn Fe (ox)3] is 7.81 BM. The compound has higher magnetic momentIIIIIthan the previously reported compound with different organic cation, [N(n-C5H11)4][Mn Fe (ox)3]. This behavior mightbe associated with the decreasing range among layers on polymeric network.Keywords: Binuclear complex; oxalato network; iron complex; magnetic properties; X-ray powder diffractionABSTRAKIIIIIKompleks Binuklir, [N(n-C4H9)4][Mn Fe (ox)3] (ox oxalate), telah disintesis dan dikarakterisasi. KompleksIIIIIbinuklir dengan formula, [N(n-C4H9)4][Mn Fe (ox)3] disintesis melalui pembentukan precursor kristal K3[Fe(ox)3] yangselanjutnya dilakukan penambahan mangan klorida dan tetrabutil ammonium klorida. Padatan hasil sintesisdikarakterisasi dengan analisis unsur, teknik difraksi sinar-X (XRD), spektroskopi FTIR dan Suseptibilitas magnetikbalans. Pada penelitian ini diketahui bahwa moment magnetik kompleks binuklir adalah 7,81 BM. Nilai momentmagnetik senyawa ini lebih tinggi dari yang dilaporkan sebelumnya dengan kation yang berbeda, [N(nIIIIIC5H11)4][Mn Fe (ox)3]. Sifat magnetik yang lebih tinggi ini dihubungkan dengan menurunnya jarak antar lapisanpada jejaring polimer.Kata Kunci: Kompleks binuklir; jejaring oksalat; kompleks besi; sifat magnetik; difraksi sinar-XINTRODUCTIONMolecular magnet based on polynuclear complexeshas superior magnetic properties than mononuclearcomplexes. For example, the magnetic moment of [N(nIIIIIC5H11)4][Mn Fe (Ox)3] is 7.5 BM [1], while the magneticmoment of its respective mononuclear complexK3Fe(Ox)3 is 5.8 BM [2]. Interactions among metal ionsin the polynuclear complex improve their total magneticmoment.The magnetic moment of polynuclear complexes isa function of the size of organic cation. Decreasing thecation size will increase the magnetic moment followedby the increase in temperature of paramagneticantiferomagnetic transition.Studies on the effect of organic cation size tomagnetic moment of polynuclear complexes have beenreported. For an example, Mathoriene et al. II[Mn Fe (ox)3]hadparamagnetic-antiferomagnetic* Corresponding author. Tel/Fax : 62-81572535690Email address : fahimahm@chem.its.ac.idFahimah Martak et al.transition at 27 K and effective magnetic moment 7.71BM. The crystal structure of the complex wasinvestigated later [3]. Tetra-Butylamine [N(n-C4H9)4] is an organiccation which is smaller than tetra-pentylamine, [N(n C5H11)4] . Therefore, when the former cation replacesIIIIIthe [N(n-C5H11)4] in [N(n-C5H11)4][Mn Fe (Ox)3], themagnetic moment of the complex will increase. Thispaper reports the research results of the substitutionand its effect on the complex magnetic moment. Thepolyanion complex was synthesized from K3Fe(Ox)3precursor.EXPERIMENTAL SECTIONMaterialsAll chemicals were reagent grade and were usedas commercially obtained, such as MnCl2.4H2O,[(NH4)2Fe(H2O)2(SO4)2].4H2O, H2SO4 6M, methanol,
90Indo. J. Chem., 2012, 12 (1), 89 - 93Fig 1. X-Ray difraction of K3[Fe(ox)3].3H2OFig 2. The spectrum of K3[Fe(ox)3].3H2OTable 1. Comparison of characteristic peaksK3[Fe(ox)3].3H2O which was synthesized and matched to3standard reference of [Fe(C2O4)3]Cautiously the mixture was heated to boiling and thenallowed the yellow precipitate of iron(II) oxalate,FeC2O4.2H2O, to settle. The precipitate was washedwith 30 mL water by decantation. A warm solution of6.62 g potassium oxalate monohydrate in 18 mL ofaquadest was added. 10 mL hydrogen peroxide wasadded, the solution was stirred continuously and thetemperature was kept below 40 C. Then the mixturewas heated, the brown precipitate was formed.Saturated solution of 1.62 g oxalic acid dihydrate in13 mL of aquadest was added until the precipitate justredisolved. The solution was filtered, and then 20 mL ofmethanol was added. It was left to crystallize in thedark. When the green crystal of the complex hasappeared, the solution filtered and the crystals werewashed in ethanol, then with acetone. The crystalswere allowed to dry at room temperature in the dark.The product was stored in glass specimen tube andwrapped in aluminium foil [4].2θK3[Fe(ox)3].3H2OStandart reference of3which was 2O, K2C2O4.H2O, H2O2, tetra-butyl ammoniumchloride and aquadest.InstrumentationMetal content was determined by AbsorptionAtomic Spectroscopy Shimadzu AA8801S. Elementalanalyses (C, H, N) were performed on Fison EA 1108microanalytical analyzer at Universiti KebangsaanMalaysia. The FT-IR spectra was recorded on Shimadzu-1FTIR-8400 spectrometer in the 4000 – 400 cm spectralregions and Absorption Atomic Spectroscopy at InstitutTeknologi Sepuluh Nopember, Powder X-ray diffractionmeasurements was performed Philip X’Pert PN-1830 XRay, at Research Center Institut Teknologi SepuluhNopember while magnetic susceptibility was measuredby Magway MSB from Sherwood Scientific LTD atUniversitas Airlangga.Synthesis Complex Binuclear [N(n-C4H9)4][MnFe(ox)3]An aqueous solution of 0.34 g MnCl2.4H2O in10 mL of aquadest was added dropwise to an aqueoussolution 0.99 g of K3[Fe(ox)3].3H2O in 10 mL aquadestat room temperature. The solution was evaporated atambient temperature for 1 h. An aqueous of tetrabutylammonium chloride was then slowly added to thesolution during stirring. After approximately 12 h, theproduct was collected by filtration, washed with H2Oand EtOH, and dried in vacuo [5].ProcedureRESULT AND DISCUSSIONSynthesis Complex K3[Fe(ox)3].3H2O10.06 g ammonium ferrous sulphate hexahydratewas dissolved in 30 mL of hot water and acidified withdilute sulphuric acid. A hot solution of 6.36 g of oxalicacid dihydrate in 50 mL of aquadest was added.Complex K3[Fe(ox)3].3H2OFahimah Martak et al.This complex is synthesized on two phases. Thefirst phase is a synthesis of Fe(II)oxalate complex. Thesecond phase is a forming of green crystalline
91Indo. J. Chem., 2012, 12 (1), 89 - 93Table 2. The metal ion and C, H and N contents of binuclear complexCompoundIIIII[N(n-C4H9)4][Mn Fe *2.352.69**Calculated-1-11688 cm , and for (Fe-O) bands at 472 cm [7]. Thespectrum of the complex is shown in Fig. 2.-1The absorption peak at 3688.02 cm is indicatedby a stretching vibration of OH. Stretching vibration-1C O from oxalate is showed at 1658.84 cm .Stretching vibration Fe-O has been observed at 459.07-1cm . This spectrum is similar to spectrum which wasreported [6]. It is indicated that K3[Fe(ox) 3].3H2O hasformed.IIIIIBinuclear Complex [N(n-C4H9)4][Mn Fe (ox)3]IIIIIIIFig 3. X-Ray Difraction of [N(n-C4H9)4][Mn Fe (ox)3]Table 3. The characteristic peaks of [N(nIIIIIIIIIIC4H9)4][Mn Fe (ox)3] and [N(n-C5H11)4][Mn Fe (ox)3]2θBinuclear ComplexIIIII[N(nC4H9)4][Mn Fe (ox)3]11.97 14.71; 17.1318.8; 19.9921.30; 22.1324.09Binuclear ComplexIIIII[N(nC5H11)4][Mn Fe (ox)3]11.89; 12.2312.98; 13.0114.79; 16.8618.43; 19.5121.07; 22.0823.95K3[Fe(ox)3].3H2O complex.The reaction of the process is represented asfollows:The K3[Fe(ox)3].3H2O complex was used asprecursor to get binuclear complex [N(n-C4H9)4]IIIII[Mn Fe (ox)3]. However, the binuclear complex wasfurther characterized by X-Ray Powder Diffraction. It islisted in Fig. 1.The Diffractogram of K3[Fe(ox)3].3H2O has similarpattern to iron(III) oxalate’s diffraction on 14-0807International Centre for Diffraction Data Reference. Thecharacteristic peaks of K3[Fe(ox)3].3H2O which weresynthesized and matched to standard reference of3[Fe(C2O4)3] is listed Table 1.The formula of the compound is also supported by-1infrared spectrum. The absorption peak at 3560 cmindicated by a stretching vibration of OH [6], Stretchingvibration C O from free oxalate ligand is shown atFahimah Martak et al.IIIBinuclear complex [N(n-C4H9)4][Mn Fe (ox)3]was synthesized by forming precursor K3[Fe(ox)3]which was followed by adding manganese chloride and tetrabutyl ammonium [N(n-C4H9)4] , solvened byaquadest as solvent. Yellow crystalline binuclearIIIIIcomplex [N(n-C4H9)4][Mn Fe (ox)3] was resulted fromthis reaction.The reaction of the process is represented asfollows:The formula of the complex resulted fromelemental content is listed in Table 2. This table showsthat the content of binuclear complex experimentsuitable to the calculated content of binuclear complexIIIII[N(n-C4H9)4][Mn Fe (ox)3].This complex was further characterized by X-RayPowder Diffraction. They are listed in Fig. 3.The diffraction pattern of the complex wassuitabletobinuclearcomplex[N(n-C5H11)4]IIIII[Mn Fe (ox)3] which was reported [9]. The peaks ofthese diffraction complexes, (2θ) 12.23; 12.98 and13.01 have different areas with binuclear complexIIIII[N(n-C5H11)4][Mn Fe (ox)3]. It is caused by differentIIIIIcation organic on complex binuclear [Mn Fe (ox)3], soit influences the distance of interlayers on polymericnetwork. The characteristic peaks of [N(n-C4H9)4]IIIIIIIIII[Mn Fe (ox)3] and [N(n-C5H11)4][Mn Fe (ox)3], arelisted in Table 3.These similar characteristic peaks of binuclearIIIIIcomplex [N(n-C4H9)4][Mn Fe (ox)3]} and [N(n-C5H11)4]IIIII[Mn Fe (ox)3]} indicated that both of their interlayerstructures are similar too. So, it means that the spaceIIIIIgroup of binuclear complex [N(n-C4H9)4][Mn Fe (ox)3]}is P6(3) and it comprises two layers which wasreported [9].
92Indo. J. Chem., 2012, 12 (1), 89 - 93IIIIITable 4. Infrared spectrum of binuclear complex [N(n-C4H9)4][Mn Fe (ox)3]Function GroupνC O oxalate as bridge ligandνC H butyl which was bonding to ammoniumMn-OFe-OAbsorbtion Areas-1(cm netic Properties of complex [N(n-C4H9)4][MnIIIFe (ox)3]IIIIIFig 4. Spectrum of [N(n-C4H9)4][Mn Fe (ox)3]The complex was analyzed by infrared spectrum tosupport the formula. The spectrum of the function groupto support the formula was reported. Stretching vibrationC O indicated oxalate as bridge ligand at 1627, 1330-1and 800 cm [10-11]. Stretching and bending vibrationC-H aliphatic from tetra butyl was been observed at-12936.6 and 1432 cm . The bands at frequency 472.7-1and 410.9 cm indicated bond between Fe-O and Mn-O[12]. The spectrum of the complex is shown in Fig. 4.The analysis of infrared spectrum can indicate thefunction group of binuclear complex [N(n-C4H9)4]IIIII[Mn Fe (ox)3], which is listed is Table 4.-1The absorption at 2970.48 cm indicates stretchingvibration of C-H butyl which was bonding to ammonium.At the same time, (CO) stretching at 1627.97; 1346.36;-1and 898. 86 cm shifted to lower frequency suggeststhat oxalate as bridge ligand. Another band appeared in-1spectra of the complex at 408.92 and 486.08 cm is dueto stretching vibration Mn-O and Fe-O.The further analysis of binuclear complex [N(nIIIIIC4H9)4][Mn Fe (ox)3] which was a synthesis showedIIsimilar result to binuclear complex [N(n-C5H11)4][MnIIIFe (ox)3] was reported previously, so we can infer thatthe complex has been formed The similar characteristicIIIIIof both [N(n-C5H11)4][Mn Fe (ox)3] and [N(n-C4H9)4]IIIII[Mn Fe (ox)3] suggests that their structures are similartoo.Fahimah Martak et al.IIMagnetism of the bimetallic tris-oxalato [N(nIIIIIC4H9)4][Mn Fe (ox)3] can be observed by analyzing themoment of magnetic value by Magnetic SusceptibilityBalances.The value of moment magnetic complex wasmeasured at 7.81 BM. This value having higher valueIIIIIthan binuclear complex [P(n-C5H11)4][Mn Fe (ox)3] wasreported [13] giving value of 7.71 BM. This proves thatdecreasing range among layers on polymeric network by substituting organic cation [P(n-C5H11)4] with [N(n C4H9)4] can increase compound magnetic interaction.The calculated magnetic moment related to theIIIIIspin of metal ion. In this case, Mn and Fe give anumber of spins which is calculated as followsST SFe SMn (SFe 5/2; SMn 5/2). The producedIIIIIbinuclear complex [N(n-C4H9)4][Mn Fe (ox)3 is highspin. This indicates that binuclear complex [N(n-C4H9)4]IIIII[Mn Fe (ox)3 is paramagnetic.It was reported [13] that complex with[MnFe(ox)3] anionic gave antiferomagnetic interaction.The magnetic moment calculated for this interaction1/2was represented as g(ST(ST-1) (g 2.00023). Thisequation gives effective moment of [N(n-C4H9)4][MnFe(ox)3] at 8.94 BM.The magnetic moment of bimetallic tris-oxalatoIIIIIwith [Mn Fe (ox)3] anionic and organic cation, [N(n C4H9)4] or [N(n-C5H11)4] was reported [13] givinglower value than the magnetic moment calculated. Itcaused [MnFe(ox)3] anionic having different metal ionsbut the same spin, SMn SFe 5/2. This gives alternativenonchollinear chirality, so it makes spin canting andgives different value of gyromagnetic (g) value, whichinfluences the magnetic moment calculated [14].CONCLUSIONThe analyzed infrared, X-Ray Diffraction andmicroanalysis conclude that the binuclear complexIIIII[N(n-C4H9)4][Mn Fe (ox)3] has been formed. Thesecomplex was synthesized by forming precursorK3[Fe(ox)3] which is followed by adding manganesechloride and tetrabuthylammonium. The value of
Indo. J. Chem., 2012, 12 (1), 89 - 93magnetic moment complex was measured at 7.81 BM.This value having higher value than binuclear complexIIIII[N(n-C5H11)4][Mn Fe (ox)3] was reported [12] whichgives value 7.71 BM. This thing proves that decreasingrange among layers on polymeric network with substituting organic cation [N(n-C5H11)4] with [N(n C4H9)4] can increase compound magnetic interaction.IIIIIBinuclear complex [N(n-C4H9)4][Mn Fe (ox)3 which isproduced is high spin. This indicates that binuclearIIIIIcomplex [N(n-C4H9)4][Mn Fe (ox)3 is paramagnetic.ACKNOWLEDGEMENTAuthors thank for financial support from HibahPenelitian PHKI Tema B, Research Grant No.06960/I2.38/LL/2009, as well as Program Studi KimiaInstitut Teknologi Sepuluh Nopember, UniversitasAirlangga, Universiti Kebangsaan Malaysia for providingfacilities and support to the success of the study.REFERENCES1. Thomas, A.M., Neelakanta, G., Mahadevan, S.,Nethaji, M., and Chakravarty, A.R., 2002, J. Inorg.Chem., 2002, 10, 2720–2726.2. Basolo, F., and Johnson, R.C., 1964, CoordinationChemistry, The Chemistry of Metal Complexes, W.ABenjamin Inc, California.3. Nuttall, C.J., and Peter D., 1999, J. Solid StateChem., 147, 3–10.4. Mathoniere, C., Nutall, C.J., Carling, S.G., and Day,P., 1996, Inorg. Chem., 35, 5, 1201-1206Fahimah Martak et al.935. Coronado, E., Galán-Mascarós, J.R., GómezGarzia, C.J., Martinez-Agudo, J.M., MartinezFerrero, E., Waerenborgh, J.C., and Almeida, M.,2001, J. Solid State Chem., 159, 2, 391–402.6. Edwards, H.G.M., and Russell N.C., 1998, J. Mol.Struct., 443, 1-3, 223–231.7. Nakamoto, K., 1997, Infrared and Raman Spectrathof Inorganic and Coordination Compounds, 5 ed.,John Willey and Sons., Inc., New York8. Andres, R., Brissard, M., Gruselle, M., Train, C.,Vaissermann, J., Malézieux, B., Jamet, J-P., andVerdaguer, M., 2001, Inorg. Chem., 40, 18, 4633–4640.9. Triki, S., Bérézovsky, F., Pala, J.S., Coronado E.,Gomez-Garcia, C.J., Clemente, J.M., Riou, A., andMolinie P., 2000, Inorg. Chem., 39, 17, 3771–3776.10. Feyerherm R., Loose, A. Lawandy, M.A., and Li, J.,2002, J. Phys. Chem. Solids, 63, 1, 71–73.11. Martak, F., Onggo, D., Ismunandar, Nugroho, A.A.,and Yamin, B.M., 2009, Curr. Res. Chem., 1, 1, 1–7.12. Coronado, E. Galán-Mascarós, J.R., Gimenez-SaizC., Gómez Garzia, C.J., Martinez-Agudo, J.M., andMartinez-Ferrero, E., 2003, Polyhedron, 22, 2381–2386.13. Ovanesyan, N.S., Shilov, G.V., Pyalling, A.A.,Train, C., Gredin, P., Gruselle, M., Kiss, L.F., andBottyan, L., 2004, J. Magn. Magn. Mater., 272-276,Part 2, 1089–1090.14. Real, J.A., Gaspar, A.B., Virginie N., and Munoz,M.C., 2003, Coord. Chem. Rev., 236, 1-2, 121–141.
Kompleks Binuklir, [N(n-C 4 H 9) 4][Mn IIFeIII(ox) 3] (ox oxalate), telah disintesis dan dikarakterisasi. Kompleks binuklir dengan formula, [N(n-C 4 H 9) 4][Mn IIFeIII(ox) 3] disintesis melalui pembentukan precursor kristal K 3 [Fe(ox) 3] yang selanjutnya dilakukan penambahan mangan klorida dan tetrabutil ammonium klorida. Padatan hasil sintesis
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