Synthesis and Characterization of New Copper (II) Complexes with mixed ligand of Heterocyclic Dithiocarbamates and 4-picoline,luitidine ,en,(1- 10)phen,pph3

New copper (II) complexes containing mixed ligands of the general formula [Cu(4Hydrpipdtc)2L2] and [Cu(4-methylpipdtc)2L2], where (4-Hydrpipdtc), (4-methylpipdtc)=4hydroxylpiperidinedithiocarbamate , 4-methylpiperidinedithiocarbamate respectively and L= 4-picoline ,luitidine ,en ,(1-10)phen,PPh3 , have been prepared and characterized by elemental analyses ,conductivity , infrared ,electronic spectra and susceptibility measurements . From the obtained data a square planar geometry was suggested for the bis (dithiocarbamato) copper (II) complex and octahedral geometry for the others has been suggested. Keyword: Heterocyclic ,Dithiocarbamates, Copper (II) , Complexes , mixed ligand Kirkuk University Journal /Scientific Studies (KUJSS) Volume 11, Issue 1, March 2016 , p.p(114-123) ISSN 1992 – 0849 Web Site: www.kujss.com Email: kirkukjoursci@yahoo.com, kirkukjoursci@gmail.com 115 يئانثلا ساحنمل ةديدج تادقعم صيخشتو ريضحت عم تادنكيل نم جيزم يئانث تيمبراكوياث و 4 (, نيما يئانث نيمثا, نيدتويل ,نيلوكيب 1 11 نيلورثونيف ) نيفسوف لينف يثلاث, دمحم دمحأ نسح 1 , راتخملا نيدلا زع دعس 2 1 ءايويكلا نسق / مولعلا ةيلك / كوكرك ةعهاج 1 Hassanahmed88@yahoo.com 2 ءايويكلا نسق / مولعلا ةيلك / لصوولا ةعهاج 2 Saadal_mukhtar@yahoo.com :ثحبلا ملاتسا خيرات 24 / 6 / 2015 :ثحبلا لوبق خيرات 22 / 10 / 2015 صخمملا ت مت ريضح مل ةديدج تادقعم ساحن ةماعلا اهتغيص ةطمتخم تادنكيل نمضتت [Cu(4-Hydrpipdtc)2L2] و [Cu(4methylpipdtc)2L2] ح ي ث نا (4-Hydrpipdtc), و (4-methylpipdtc) = 4-hydroxylpiperidinedithiocarbamate و 4-methylpiperidinedithiocarbamate و يلاوتلا ىمع L = 4-picoline ,luitidine ,en ,(1-10)phen,PPh3 تصخشو ةرضحملا تادقعملا رصانعلا ليمحت ةطساوب ءا رمحلا تحت ةعشلاا فايطاو ةيميصوتلا تاسايقو ةيئرملاو نمو ةيسيطانغملا ةيساسحلا تاسايقو ةيجسفنبلا قوفلاو ( ساحن تيمبراكوياث ياد سب دقعممل يوتسملا عبرملا لكشلا حا رتقا مت جئاتنلا II ) تادقعممل حوطسلا ينامث لكشلاو ىرخلاا . تاممكلا : ةلادلا ةطمتخم تادنكيل , تيمبراكوياث يئانث , ةسناجتم ريغ تاقمح , ساحنلا تادقعم . Kirkuk University Journal /Scientific Studies (KUJSS) Volume 11, Issue 1, March 2016 , p.p(114-123) ISSN 1992 – 0849 Web Site: www.kujss.com Email: kirkukjoursci@yahoo.com, kirkukjoursci@gmail.com 116 1 .Introduction Recently, the design and synthesis of coordination complexes have attracted much attention due to their diversity structures as well as potential applications as functional materials and enzymes.[1] Therefore, all kinds of ligands containing nitrogen, oxygen, sulfur or phosphorus are used to synthesize the coordination complexes[2]. Metal dithiocarbamate complexes have been extensively studied. Monomeric, dimeric, polymeric, two-dimensional and three-dimensional structures are all featured amongst these complexes. In copper dithiocarbamate complexes, the copper oxidation states I–III have been accessible[3] because dithiocarbamates have capability to stabilize transition metals in a wide range of oxidation states [4].Some copper (II) complexes with dithiocarbamates have also been reported. Pyrrolidinedithiocarbamate (PDTC) has been shown to exhibit antioxidant, antiviral and antiinflammatory properties and metal transport in membranes [5]. 2. Experimental Materials and Instrumentation All reagents and solvents were commercially available high grade materials (Fluka A.G., Riedel-de Haën, BDH) and used as received, Infrared spectra were recorded on a Brucker Tensor 27co. FTIR spectrophotometer in the 400-4000 cm -1 range using KBr discs Conductivity measurements were carried out on 10 -3 M solution of the complexes in DMF using conductivity meter PCM3 Jenway at an 25 ο temperature. The electronic spectra were recorded on a Shimadzu UV-visible spectrophotometer UV-160 for 10 -3 M solutions of complexes in DMF as solvent at 25°C using 1 cm quartz cell. Metal content was determined spectrophotometrically using AA670 atomic absorption spectrophotometer. Melting points were recorded on an Electrothermal 9300 apparatus. The magnetic measurements were carried out at 25°C on the solids by Faraday’s method using Brucker BM6 instrument. I.A. Preparation of sodium 4-hydroxyl piperidinedithiocarbamate, Na(4-hpipdtc) 4-hydroxyl piperidine (1.01 g, 0.01 mol) was dissolved in 30 ml of water and the resulting solution was cooled in an ice-salt bath. Sodium hydroxide (0.4 g, 0.01 moles) was added to this solution under stirring, followed by carbon disulfide (0.76 g, 0.01 mol). The mixture was stirred for 30 min in the ice-salt bath, then allowed to reach room temperature and stirred for an additional one hour then dried under vacuum. A yellowish white precipitate formed . Kirkuk University Journal /Scientific Studies (KUJSS) Volume 11, Issue 1, March 2016 , p.p(114-123) ISSN 1992 – 0849 Web Site: www.kujss.com Email: kirkukjoursci@yahoo.com, kirkukjoursci@gmail.com 111 I.B. Preparation of 4-methyl piperidinum 4-methylpiperidinedithiocarbamate [S2CNC6H12][H2NC6H12]. The ligand prepared in different method 4-methylPiperidine (9.91g, 0.1 mol) was dissolved in water (20 mL), and carbon disulfide (7.6g, 0.1mol) was added. The reaction was stirred for2 h. Chloroform (80 ml) was added and, after vigorous stirring, the aqueous layer discarded. Reduction in solvent volume led to precipitation of an off-white product. Then dried under vacuum. I.C. Synthesis of complex [Cu (4-hydpipdtc) 2] To a solution of sodium 4-hydroxylpiperidinedithiocarbamic (0.5 g, .0025mol) in methanol was added a methanolic solution of CuCl2.2H2O (0.203 g, 0.0012 mol) drop wise with constant stirring at room temperature . After 30 min the black precipitate was filtered off and then dried in air. I.D. Synthesis of complex [Cu (4-hydpipdtc) 2L2] Prepared as in procedure (I.C) using the same weight of metal salt above and after the formation of the precipitate, (0.0025 mol) of(triphenylphosphine) or (4picoline) or (3,5lutidine) was added with continuous stirring for 30min, the complex separated out, were filtered, washed with methanol 10 ml then dried under vacuum. I.E. Synthesis of complex [Cu (4-hydpipdtc) 2L] Prepared similarly as in procedure (Ι.C) using the same weight of metal salt above and after the formation of the precipitate,(0.0012 mol) of (1,10-phenanthroline or ethylenediamine) was added with continuous stirring for 30 min. The complex formed was filtered and washed with methanol 10 ml, then dried under vacuum. I.F. Synthesis of complex [Cu (4-methylpipdtc) 2] Prepared by the same procedure as for I.Cusing [S2CNC6H12][H2NC6H12] (1.0 g, 0.003)mol , CuCl2 2H2O ( 0.254g ,0.0015mol) to formed a black product . I.G. Synthesis of complex [Cu (4-methylpipdtc) 2L2] Prepared by the same procedure as for I.F using the same weight of metal salt above after the formation of the precipitate, (0.003 mol) of (triphenylphosphine) or (4picoline) or (3,5lutidine) was added with continuous stirring for 30min, the complex separated out, were filtered, washed with methanol 10 ml then dried under vacuum. Kirkuk University Journal /Scientific Studies (KUJSS) Volume 11, Issue 1, March 2016 , p.p(114-123) ISSN 1992 – 0849 Web Site: www.kujss.com Email: kirkukjoursci@yahoo.com, kirkukjoursci@gmail.com 111 I.H. Synthesis of complex [Cu (4-methylpipdtc) 2L] Prepared by the same procedure as for I.F using the same weight of metal salt above after the formation of the precipitate,(0.0015mol) of (1,10-phenanthroline or ethylenediamine) was added with continuous stirring for 30 min.The complex formed was filtered and washed with methanol 10 ml, then dried under vacuum. 3. Results and discussion The ligand was prepared by the reaction of carbon disulfide with the secondary amine 4hydroxypiperidine in the presence of sodium hydroxide and the complexes were prepared by direct addition of the aqueous solution of the copper chloride to the ligand solution in aqueous methanol, using 1:2 (metal: ligand) molar ratio. The base adducts were prepared by adding the base to the prepared bis-complexes in (1:2) or (1:1) molar ratios. Scheme (1).


.Introduction
Recently, the design and synthesis of coordination complexes have attracted much attention due to their diversity structures as well as potential applications as functional materials and enzymes. [1] Therefore, all kinds of ligands containing nitrogen, oxygen, sulfur or phosphorus are used to synthesize the coordination complexes [2]. Metal dithiocarbamate complexes have been extensively studied. Monomeric, dimeric, polymeric, two-dimensional and three-dimensional structures are all featured amongst these complexes. In copper dithiocarbamate complexes, the copper oxidation states I-III have been accessible [3] because dithiocarbamates have capability to stabilize transition metals in a wide range of oxidation states [4].Some copper (II) complexes with dithiocarbamates have also been reported.
Pyrrolidinedithiocarbamate (PDTC) has been shown to exhibit antioxidant, antiviral and antiinflammatory properties and metal transport in membranes [5].

Materials and Instrumentation
All reagents and solvents were commercially available high grade materials (Fluka A.G., Riedel-de Haën, BDH) and used as received, Infrared spectra were recorded on a Brucker Tensor 27co. FTIR spectrophotometer in the 400-4000 cm -1 range using KBr discs Conductivity measurements were carried out on 10 -3 M solution of the complexes in DMF using conductivity meter PCM3 Jenway at an 25 ο temperature. The electronic spectra were recorded on a Shimadzu UV-visible spectrophotometer UV-160 for 10 -3 M solutions of complexes in DMF as solvent at 25°C using 1 cm quartz cell. Metal content was determined spectrophotometrically using AA670 atomic absorption spectrophotometer. Melting points were recorded on an Electrothermal 9300 apparatus. The magnetic measurements were carried out at 25°C on the solids by Faraday's method using Brucker BM6 instrument.

I.A. Preparation of sodium 4-hydroxyl piperidinedithiocarbamate, Na(4-hpipdtc)
4-hydroxyl piperidine (1.01 g, 0.01 mol) was dissolved in 30 ml of water and the resulting solution was cooled in an ice-salt bath. Sodium hydroxide (0.4 g, 0.01 moles) was added to this solution under stirring, followed by carbon disulfide (0.76 g, 0.01 mol). The mixture was stirred for 30 min in the ice-salt bath, then allowed to reach room temperature and stirred for an additional one hour then dried under vacuum. A yellowish white precipitate formed . The ligand prepared in different method 4-methylPiperidine (9.91g, 0.1 mol) was dissolved in water (20 mL), and carbon disulfide (7.6g, 0.1mol) was added. The reaction was stirred for2 h. Chloroform (80 ml) was added and, after vigorous stirring, the aqueous layer discarded. Reduction in solvent volume led to precipitation of an off-white product. Then dried under vacuum.

I.C. Synthesis of complex [Cu (4-hydpipdtc) 2 ]
To a solution of sodium 4-hydroxylpiperidinedithiocarbamic (0.5 g, .0025mol) in methanol was added a methanolic solution of CuCl 2 .2H 2 O (0.203 g, 0.0012 mol) drop wise with constant stirring at room temperature . After 30 min the black precipitate was filtered off and then dried in air.

I.D. Synthesis of complex [Cu (4-hydpipdtc) 2 L 2 ]
Prepared as in procedure (I.C) using the same weight of metal salt above and after the formation of the precipitate, (0.0025 mol) of(triphenylphosphine) or (4-picoline) or (3,5lutidine) was added with continuous stirring for 30min, the complex separated out, were filtered, washed with methanol 10 ml then dried under vacuum.

I.E. Synthesis of complex [Cu (4-hydpipdtc) 2 L]
Prepared similarly as in procedure (Ι.C) using the same weight of metal salt above and after the formation of the precipitate,(0.0012 mol) of (1,10-phenanthroline or ethylenediamine) was added with continuous stirring for 30 min. The complex formed was filtered and washed with methanol 10 ml, then dried under vacuum.

I.F. Synthesis of complex [Cu (4-methylpipdtc) 2 ]
Prepared by the same procedure as for I.

I.G. Synthesis of complex [Cu (4-methylpipdtc) 2 L 2 ]
Prepared by the same procedure as for I.F using the same weight of metal salt above after the formation of the precipitate, (0.003 mol) of (triphenylphosphine) or (4-picoline) or (3,5-lutidine) was added with continuous stirring for 30min, the complex separated out, were filtered, washed with methanol 10 ml then dried under vacuum.

Scheme (1): Synthesis of ligands, Cu(II) dithiocarbamate complexes, and their Adducts
The composition and analytical data for all complexes are given in Table 1; IR and UV-Visible spectra data are giving in

Infrared spectra measurements
The most significant bands recorded in the FT-IR spectra of the ligand and the complexes are reported in Table 2. For dithiocarbamate compounds, three main regions of IR spectra are of interest. First, the 1580-1450 cm -1 region, which is primarily associated with the stretching .

UV-Visible spectroscopy
The UV spectra of the 1,2 ligands showed absorption band at32187,31847cm -1 assigned to the transition n→ π * and π → π * respectively. The complexes 3, 9 show a broad band at

Conclusion
From the above discussions the following structures were suggested which indicate a four coordinate geometry around the metal ion with a bidentate coordination ligand through two sulphur atoms Fig. (1) expected have a square planar geometry.
The other six coordinate complexes suggest the coordination via four sulphur atoms of the two 4-substituted piperidinedithiocarbamte ligands and two nitrogen of N-base or two phosphorus atoms of PPh 3 Fig. (2) expected a octahedral geometry.