Synthesis and Characterization of Mn+2, Co+2, Ni+2, Cu+2 and Zn+2

ABSTRACT

A series of new complex salts of the type [A]2[MCl2I2] where A=1,3,5- trimethylpyridinium cation, M= Mn+²,Co+², Ni+²,Cu+² and Zn+² were prepared by the reaction of the metal chloride and 1,3,5-trimethylpyridinium iodide in (1:2) molar ratio and characterized by elemental analysis, molar conductance, IR, Uv/Vis., spectral studies and magnetic measurements. The crystal structure of 1,3,5-trimethylpyridinuim iodide was determined by single crystal x-ray crystallography.

The structure of the anion part and a 1,3,5- trimethylpyridinium cation which crystallizes in the orthorhombic space group (Cmcm) with a=8.9850(9), b=15.767(2), c=6.9940(6)A°, V=990.82 (16)A°, Z=4. Which is on a crystallographic mirror plane perpendicular to C-axis except for methyl hydrogen atoms. The anion and cation are connected through hydrogen bonds between I and the cation by hydrogen bonding, electrostatic interaction and weak - interaction are also expected.

Keywords: Pyridinium Salt, Crystal Structure of 1,3,5-Trimethylpyridinium Iodide.

ﺢﻠﻤ ﻊﻤ Zn+² ﻭ Cu+² Ni+2، Co+2، ﻟﺍ ﺕﺍﺩﻘﻌﻤ ﺹﻴﺨﺸﺘ ﻭ ﺭﻴﻀﺤﺘـMn+2 ،

ﻡﻭﻴﻨﻴﺩﻴﺭﺒﻟﺍ، ﻟ ﻱﺭﻭﻠﺒﻟﺍ ﺏﻴﻛﺭﺘﻟﺍ ـ1 ،3،ﺩﻴﺩﻭﻴﺍ ﻡﻭﻴﻨﻴﺩﻴﺭﺒ ﻝﻴﺜﻤ ﻲﺜﻼﺜ -5

ﺹﺨﻠﻤﻟﺍ

1 = A،3، ﺜﻼﺜ-5ـﻲ ﻨﻋـﺎﻤﺩ 2[MCl2I2][A] ﺔﻐﻴﺼﻟﺍ ﺕﺍﻭﺫ ﺓﺩﻘﻌﻤﻟﺍ ﺡﻼﻤﻻﺍ ﻥﻤ ﺔﻋﻭﻤﺠﻤ ﺭﻴﻀﺤﺘ ﻡﺘ

+2

ﻠﻋﺎﻔﻤ ﻝﻼﺨ ﻥﻤـ ﻴﺭﻭﻠﻛ ﺔـ ﻠﻔﻟﺍ ﺕﺍﺩـﺕﺍﺯ Zn+² ﻭ Cu+² Ni+2، Co+2، ، ﺩﻴﺩﻭﻴﺍ ﻡﻭﻴﻨﻴﺩﻴﺭﺒ ﻝﻴﺜﻤ،=M Mn 1ﻭ،3، ﺴﺍﻭﺒ ﺕﺍﺩﻘﻌﻤﻟﺍ ﺹﻴﺨﺸﺘ ﻡﺜ .(1:2) ﺔﻴﻟﻭﻤ ﺔﺒﺴﻨﺒ ﺩﻴﺩﻭﻴﺍ ﻡﻭﻴﻨﻴﺩﻴﺭﺒ ﻝﻴﺜﻤ ﻲﺜﻼﺜ-5ـ ﻴﻠﺤﺘﻟﺍ ﺔﻁـ ﻟﺍ ﻝـﻕﻴﻗﺩ ﺭﺼﺎﻨﻌﻠﻟ،ﻲﺌﺎﺒﺭﻬﻛﻟﺍ ﻝﻴﺼﻭﺘﻟﺍ ،ﺩﺎﺠﻴﺍ ﻡﺘ .ﺔﻴﺴﻴﻁﺎﻨﻐﻤﻟﺍ ﺕﺎﺴﺎﻴﻘﻟﺍﻭ ﺔﻴﺠﺴﻔﻨﺒﻟﺍ ﻕﻭﻓﻭ ﺀﺍﺭﻤﺤﻟﺍ ﺕﺤﺘ ﺔﻌﺸﻷﺍ ﻑﻴﻁ ﻟ ﻱﺭﻭﻠﺒﻟﺍ ﺏﻴﻛﺭﺘﻟﺍـ1 ،3، ﺒ ﻥﻴﺒﺘ ﺔﻴﺩﺎﺤﻻﺍ ﺓﺭﻭﻠﺒﻠﻟ ﺔﻴﻨﻴﺴﻟﺍ ﺔﻌﺸﻻﺍ ﺔﻁﺴﺍﻭﺒ ﺩﻴﺩﻭﻴﺍ ﻡﻭﻴﻨﻴﺩﻴﺭﺒ ﻝﻴﺜﻤ ﻲﺜﻼﺜ-5ـﻥﺎ 1ﺏﺠﻭﻤﻟﺍ ﻥﻭﻴﻻﺍ ﻙﻟﺫﻛﻭ ﺏﻟﺎﺴﻟﺍ ﻥﻭﻴﻻﺍ ﻥﻤ ﻥﻭﻛﺘﻴ ﺏﻛﺭﻤﻟﺍ،3، ﻠﺒﺘ ﻱﺫﻟﺍﻭ ﻡﻭﻴﻨﻴﺩﻴﺭﺒ ﻝﻴﺜﻤ ﻲﺜﻼﺜ-5ـ ﻅﻨﺒ ﺭﻭـﻡﺎ A° 6.9940(6) =c 15.767(2)=b ﻥﻴﻌﻤﻟﺍ، ﻴﻏﺍﺭﻔﻟﺍ ﺔﻋﻭﻤﺠﻤﻟﺍ ـ ﺤﻤﻟﺍ (Cmcm) ﺔـ8.9850(9) =a ﺭﻭﺎ 990.82(16)A° =V،ﺍﺩﻋ C ﺭﻭﺤﻤ ﻰﻠﻋ ﻱﺩﻭﻤﻋ ﻱﺭﻭﻠﺒ ﺓﺁﺭﻤ ﻯﻭﺘﺴﻤ ﻲﻓ ﻊﻗﺍﻭﻟﺍ ﺏﺠﻭﻤﻟﺍ ﻥﻭﻴﻻﺍ ﻥﺃ ﺫﺇ 4=Z ﻨﻫ ﻙﻟﺫﻛﻭ ﺔﻴﻨﻴﺠﻭﺭﺩﻴﻫ ﺭﺼﺍﻭﺎﺒ ﻥﺎﻁﺒﺘﺭﻤ ﺏﻟﺎﺴﻟﺍﻭ ﺏﺠﻭﻤﻟﺍ ﻥﺎﻨﻭﻴﻻﺍ .ﻝﻴﺜﻤﻟﺍ ﺔﻋﻭﻤﺠﻤ ﻥﻴﺠﻭﺭﺩﻴﻫـ ﺼﺂﺘ ﻙﺎـﺭ

.ﻊﻗﻭﺘﻤ ﻑﻴﻌﻀ ﺼﺂﺘ ﻭ ﻲﻛﻴﺘﺎﺘﺴﻭﺭﺘﻛﻴﻟﺍـ ـ ـ- ﺭ

ﻡﻭﻴﻨﻴﺩﻴﺭﺒﻟﺍ ﺢﻠﻤ :ﺔﻟﺍﺩﻟﺍ ﺕﺎﻤﻠﻛﻟﺍ، ﻟ ﻱﺭﻭﻠﺒﻟﺍ ﺏﻴﻛﺭﺘﻟﺍ ـ1 ،3،.ﺩﻴﺩﻭﻴﺍ ﻡﻭﻴﻨﻴﺩﻴﺭﺒ ﻝﻴﺜﻤ ﻲﺜﻼﺜ -5

INTRODUCTION

Considerable interest has also been shown over recently years in the transition metal halide complexes, and a among them tetrahalometalates with various organic counter cations have been subject of theoretical (Navaro et al., 2009), structural (Lozano et al., 2004) magneto-structural (Luque et al., 2002 ; Mazotto et al., 2001) and spectroscopic studies (Luque et al., 1997 ; Hitchman and Cassidy1979).

The preparation, crystal structure and solid-state properties of four tertrabromocuprate(II) salts using pyridinium and n-methylpyridinium (n=2-,3- and -4-) as counter ions were carried out as a part of studies on hybride organic/ inorganic material based copper (II) halides, in which they show the influence of the organic cation(size, shape and position of the substitutent) on the packing interactions that governed the crystal organization (Luque et al., 2001 ; Sertucta and Luque, 1998).

The design and synthesis of copper (II) bromides constitutes to receive much attention owing to their applications in fundamental and applied science, ranging from solid-state physics to bioinorganic chemistry.

A novel pyridinium salt, 2,4-bis[p-(N,N-dimethylamino) styryl]-N-methylpyridinium bromide was synthesized and characterized by TG,¹ HNMR spectroscopy and x-ray crystallography, and the reaction process was studied by using Es-Ms by Hao et al., (2004), they showed that the salt have large two photon absorption.

The nickel and platinum complexes [MX2(dppe)] (X=Cl,Br)(dppe=diphenyl phosphinoethane) react with bi- and tri-valent metal diethylditiocarbamates [M`(S2CNEt2)n], (M`=Pb, Zn, Hg, Ni, n=2, M`=Co, Fe, Mn, n=3) to afford the salts [M(S2(NEt2)2dppe][M`X4] was studied by Exarchos et al., (2001). The salts have been fully characterized by physicochemical properties and x-ray crystallography.

The salts [MeEtim]2[MCl4], [MeEtim]+=1-methyl-3-ethyl imidazolium, M=Mn,Co or Ni) are shown by EXAES to dissolve in basic [MeEtim]Cl.AlCl3 ionic liquid to yield four coordinate [MCl4]-², and dissolve in acidic [MeEtim]Cl-AlCl3 ionic liquids to yield six coordinate [M(AlCl)3]- anion (Dent et al.,1990).

Kim et al., (2003) prepared and used the [RMIM][ZnX2Y2] ionic liquid system (R=Me,Et,n-Bu,benzyl,X=Y=Cl or Br or X=Cl,Y=Br) for the coupling reaction of CO2 and ethylene or propylene oxide to produce cyclic carbonate. Crystal structure of [(M)2IM][ZnBr2Cl2]{(M)=2 dimethyl} showed that two imidazolium cations were paired with [ZnBr2Cl2].

As a part of an on-going investigation of these metallate salts, we have prepared and studied the properties of 1,3,5-trimethylpyridinium dichlorodiiodo metallate (II) salts (C8H12N)2[MI2Cl2], M=Mn+², Co+², Ni+², and Zn+². Also, the crystal structure of 1,3,5- trimethylpyridinium iodide was determined by x-ray crystallography.

EXPERIMENTAL

All starting materials were obtained commercially and used as received. The solvent were dried by allowing them to stand over 3A molecular sieves overnight. The preparation was carried out under nitrogen atmosphere. Elemental analysis (C,H,N) was performed on a Carlo Erba 1106 analyzer. Metal content analyses were made on Shimadzu AA670 atomic absorption spectrophotometer. IR spectra were recorded on an Infrared spectrophotometer bruker (Tensor 27) in the 200-4000cm-¹ range using CsI discs.

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