Reaction between a warm water mixture of pyridoxal hydrochloride (PL.HCl), and Smethyilisothiosemicarbazidehydroiodide (SMeTSC.HI) in the presence of Na2CO3&nbsp;.10 H O, we got pyridoxal S-methylisothiosemicarbazone (PLITSC; H2L). Ligand with appropriate Cu salt is coordinated, to give next complex: dark-brown, penta coordinated, square-pyramidal structure, mono(ligand)complex Cu(II) formula, [Cu(PLITSC)Br(CH3OH)]Br.In this work is given synthesis and structure of the complex with Schiff-based ligand

Ivković, S.

Jevtović, V.

English

Journal of Engineering & Processing Management (EPM)

______________________________________________________________________________________  Journal of Engineering & Processing Management|  7  7 Volume 2, No. 2, 2010  UDK 546.562 Scientific paper SYNTHESIS AND STRUCTURAL ANALYSIS OF A Cu(II) COMPLEX WITH PYRIDOXAL S-METHYLISOTHIOSEMICARBAZONE (PLITSC) LIGAND SINTEZA I STRUKTURNA ANALIZA Cu(II) KOMPLEKSA SA PIRIDOKSAL  S-METILIZOTIOSEMIKARBAZONOM (PLITSC) LIGANDOM S. Ivković1, V. Jevtović2  1 Faculty of Environmental governance and corporate responsibility, University EDUCONS,Sremska Kamenica, Serbia 2 Department of Chemistry, Faculty of Sciences, University of Novi Sad, Serbia  Izvod Reakcijom toplog vodenog rastvora piridoksal-hidrohlorida (PL·HCl) i S-metilizotiosemikarbazidhidrojodida (SMeTSC·HI), u prisustvu Na2CO3·10H2O, dobili smo piridoksal-metilizotiosemikarbazon (PLITSC; H2L). Ligand i odgovarajuća so Cu se koordinuju i obrazuju kompleks: braon-obojen, penta-koordinovan, kvadratno-piramidalne strukture, mono(ligand)kompleks Cu(II) formule [Cu(PLITSC)Br(CH3OH)]Br. U ovom radu je data sinteza i struktura kompleksa sa ligandom u neutralnoj, Zwitter jonskoj formi.  Ključne reči: Piridoksal-S-metilizotiosemikarbazon, Cu(II) kompleks, Sinteza, Kristalna struktura.  Abstract Reaction between a warm water mixture of pyridoxal hydrochloride (PL.HCl), and S-methyilisothiosemicarbazidehydroiodide (SMeTSC.HI) in the presence of Na2CO3 .10 H2O, we got pyridoxal S-methylisothiosemicarbazone (PLITSC; H2L). Ligand with appropriate Cu salt is coordinated, to give next complex: dark-brown, penta coordinated, square-pyramidal structure, mono(ligand)complex Cu(II) formula, [Cu(PLITSC)Br(CH3OH)]Br.In this work is given synthesis and structure of the complex with Schiff-based ligand. Key words: Pyridoxal-S-methylisothiosemicarbazone, Cu(II) complex, Synthesis, Crystal structure.  1. INTRODUCTION  A large number of complexes incorporating PLTSC [1] and PLSC [2,3,4] ligands has been reported, including a recent reviw [5], while only a couple of complexes incorporating PLITSC have been synthesized thus far [6]. Isothiosemicarbazide itself and his derivatives carbazons and ______________________________________________________________________________________  Journal of Engineering & Processing Management|  8  8 Volume 2, No. 2, 2010  complexes with metals are subjects of labour for a longer period of years with a bigger interest, and it was seen with a bigger number of works [7], and a monograph [8]. The reasons for this affirmation are in fact that this class of compounds is interest with aspect of different kinds of crystal compositions of rewarded complexes, and they were affirmed as biology active molecules [9]. Coordination chemistry of isothiosemicarbazones is interested because of aspects of variety ligands systems, because of their dentate, and they type of sets of donors atoms. Methodical investigations for this type of compounds with different dentate were showed, that unexpectedly, isothiosemicarbazons remnant for coordination instead atom of sulfur, it use as a rule thioamide atom of nitrogen[10,11], which was assured with a larger number of  affirmed compositions. There are many complexes with tridentate ligands which were become on base of this class of compounds, in that belong to, and mentioned, pyridoxal S-methylisothiosemicarbazone (PLITSC) with thirdentate ONN sets of donors atoms. In literature, there can be found special points about complexes Fe with the mentioned ligand in sense of  physical chemistry and voltametric properties of complex [Fe(ITSCPL)(ITSCPL-H)](NO3)3, [Fe(ITSCPL)Cl3].H2O and [Fe(ITSCPL)2]OAc.2H2O [12,13,14], and investigations which were involved for these ligands systems, and they were a topic of one doctor‘s dissertation [15].  2. EXPERIMENTAL   All comercially obtained reagent-grade chemicals were used without further purification, except for the ligands.   2.1. Synthesis of ligand PLITSC  Mixture of 2.0g (10mmol) PL.HCl and 2.30g (10mmol) SMeTSC.HI ought to pour over with 20cm3 H2O and ought to warm to complete dissolve of their parts. To warm mixture ought to add 3.0g (10mmol) Na2CO3·10H2O which was dissolved before in 20cm3 H2O. Very soon comes to sedimentation of pale-yellow fibrous crystals and after a couple hours they ought to be filtrate and washed with water and ethanol. Yield: 2.40g.  2.2. Syntheses of complex [Cu(PLITSC)Br(CH3OH)]Br  Warm 0.14g (0.5mmol) PLITSC in 10cm3 MeOH and add mixture 0.15g (0.7mmol) CuBr2 in 5cm3 MeOH. Green mixture is got which is left behind on room temperature about 50 hours, and after that comes to separation of green monocrystals. Yield: 0.13g.  2.3. Crystal structure determination  Data for complex were collected on a Philips PW1100 diffractometer with MoKα radiation [λ= 0.7107Å]. ______________________________________________________________________________________  Journal of Engineering & Processing Management|  9  9 Volume 2, No. 2, 2010  The structure was solved using direct methods SIR92  [16] and refined using SHELXL97 [17] on F2 by full matrix least squares with anisotropic displacement parameters for all non-hydrogen atoms. Details concerning crystal data and refinement are given in Table 1. Crystallographic data have been deposited with the Cambridge Crystallographic Data Base as CCDC reference number 735806 for complex.  Table 1. Crystal data and structure refinement details of complex  Empirical formula C11H18Br2Cu1N4O3S1 Formula weight 478.67 Temperature 294K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1  Unit cell dimensions a = 7.6945(4)  α= 96.86(19)° b = 9.7045(4) Å  β= 106.73(4)°. c = 13.3238(13) Å  γ= 111.520(4)° Volume 857.604 (14) Å3 Z 2   3. RESULTS AND DISCUSSION  3.1. Synthesis and structure of complexes  Pyridoxal S-methylisothiosemicarbazone (PLITSC; H2L), is synthesized according to formely described action [15], reaction with some warm water mixture pyridoxal hydrochloride (PL.HCl),[3-hydroxy-5-(hydroxymethyl)-2-methylpyridine-4-carbaldehydehydrochloride]and S- metyilisothiosemicarbazidehydroiodide (SMeTSC.HI) in presence  Na2CO3 .10 H2O (Scheme 1).  ______________________________________________________________________________________  Journal of Engineering & Processing Management|  10  10 Volume 2, No. 2, 2010  Cl-N+CH3OHHOHO+ NH2 NNH2SCH3IHN+CH3OHHOHN NNH2SCH3PL HClITSC HIH2L   Scheme 1. Synthesis of pyridoxal S-methylisothiosemicarbazone (PLITSC)  The common  coordination mode of this and ligand form of PLITSC is presented in Scheme 2, and they are taken out base of results X-ray analysis compositions PLITSC and which is in harmony with former well known compositions [14]. H2L ligand for coordination use three ligators atom: are the phenolic oxygen, hydrazine nitrogen and atom of nitrogen of the isothioamide group. In that case ONN ligand PLITSC, two metallocycles are formed: one six-membered (pyridoksilydene) and one five-membered (isothiosemicarbazide derivate). PLITSC ligand can coordinated in neutral, monoanionic or dianionic forms (Scheme 2).   N+CH3OHO-NNHSCH3NHH MN+CH3O-OHHNN SCH3NH-MNCH3OHO-NNSCH3NH-Ma) H2Lc) L 2-b) HL -  Scheme 2. Coordination models and ligand forms: a) neutral, b) mono- and c) dianionic ______________________________________________________________________________________  Journal of Engineering & Processing Management|  11  11 Volume 2, No. 2, 2010  On the picture Figure 1 is given a structure of a neuter mono(ligand)complex [Cu(ITSPL)Br(CH3OH)]Br, and in Table 2 are given the length of connections metal-ligand and angles among connections in coordinate sphere of metal.  Figure 1. The molecular structure of the complex, with the atom-and ring-labeling scheme   Table 2. Bond lengths [Å] and angles [o] for the complex  Br1-Cu 2.776(5) N(11)-Cu-N(9) 80.79(15) Cu-O6 2.008(2) N(9)-Cu-O(7) 45.84(17) Cu-O7 1.906(2) O(7)-Cu-O(6) 46.36(14) Cu-N9 1.972(2) O(6)-Cu-N(11) 95.87(16) Cu-N11 1.964(2) N(11)-Cu-Br(1) 94.97(16)   O(6)-Cu-Br(1) 93.16(14)   O(7)-Cu-Br(1) 95.25(18)   N(9)-Cu-Br(1) 103.68(15)   O(7)-Cu-N(11) 168.25(14)   O(6)-Cu-N(9) 163.09(17)   C(14)-N(10)-C(21) 125.39(5)  Penta coordinate copper in equatorial plane is surrounded with 5 atoms, three of ONN ligand and one atom oxygen O6 from methanol. Structure of square pyramid gives Br atom in the axial position. The lengths of Cu-ligand connections in equatorial plane are in the very close value. The shortest is connection of phenolic oxygen O7 (Cu-O7 1.906(2) Å). Yet, the longest connection with copper is with Br atom in axial position (Cu-Br1 2.776(5) Å). This complex has a molecule of ______________________________________________________________________________________  Journal of Engineering & Processing Management|  12  12 Volume 2, No. 2, 2010  ligand is neuter form (H2L) (see Schema 2.). Affirmation of this is presence atom of hydrogen on nitrogen N8, pyridine N10, as his value of angle which pyridine N10 has with neighbouring C atoms and it is 125.39(5)º.  4. CONCLUSION  The structure of the title compound C11H18Br2Cu1N4O3S1, is an interesting metal complex with a Schiff base derived from isothiosemicarbazide and pyridoxal (pyridoxal is a 3-hydroxy-5 hydroxymethyl-2-methylpyridine-4-carboxaldehyde). Ligand pyridoxal-Smethylisothiosemi-carbazone (PLITSC; H2L) is tridentate ONN ligand. The CuII  environment is a square pyramid coordination, the equatorial plane of which is formed by the tridentate ONN-coordinated pyridoxal-Smethylisothiosemicarbazone and one methanol molecule, while the atom Br is in the apical position. This compound crystallizes in triclinic symmetry, in space group P-1, with lattice constants: a=7.6945(4) Ǻ, b=9.7045(4) Ǻ, c=13.3238(13) Ǻ, α=96.86(19)º, β=106.73(4)˚, γ=111.520(4)˚, V=857.604(14)Ǻ3, Z=2.  Acknowledgements  This work was partly supported by the Provincial Secretariat for Science and Technological Development of AP Vojvodina.  The authors acknowledge for help Crystallography Service, Department of Physics, Faculty of Sciences, University of Novi Sad.  APENDIX AND SUPLEMENTARY MATERIAL  CCDC 735806 contains the supplementary crystallographic data for the complex. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Chambridge, CB2 1EZ, UK (fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk)    REFERENCES [1] M. Ferrari Belicchi, G.Fava Gasparri, E. Leporati, C.Pelizzi, P.Tarasconi, G.Tosi, J.Chem.Soc.Dalton Trans. (1986) pp. 2455. 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SYNTHESIS AND STRUCTURAL ANALYSIS OF A Cu(II) COMPLEX WITH PYRIDOXAL S-METHYLISOTHIOSEMICARBAZONE (PLITSC) LIGAND

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SYNTHESIS AND STRUCTURAL ANALYSIS OF A Cu(II) COMPLEX WITH PYRIDOXAL S-METHYLISOTHIOSEMICARBAZONE (PLITSC) LIGAND

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