Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Chemistry Central Journal

Samson Jegan Jenniefer¹  Packianathan Thomas Muthiah¹ 

[1] School of Chemistry, Tiruchirappalli, Tamil Nadu, 620024, India

关键词: Crystal structure;    Carboxylates;    Supramolecular architectures;    Cu (II) complexes;    Paddle wheel structures;   

Others  :  787957
DOI  :  10.1186/1752-153X-7-35

 received in 2013-01-23, accepted in 2013-02-13,  发布年份 2013

【 摘 要 】

Background

Various dinuclear copper (II) complexes with octahedral geometry have been reported. The majority of these complexes contain N containing aromatic rings as axial ligands. There are also a few cases where the solvent used in the reaction occupies the axial position of the dinuclear copper (II) complex. This may occur by planned synthesis or some times by serendipity. Here we report some four copper (II) complexes containing solvent and or N containing heterocyclic ring as the axial ligand.

Results

Four compounds, each containing dinuclear Copper (II) units (with the most robust, frequently occurring paddle wheel structures) were synthesized and characterised by single crystal X-ray diffraction and by IR spectroscopy. The compounds 1 & 2 have the general formula Cu₂(RCOO) ₄(L)₂ [(for (1) RCOO= 4-Chloro Benzoate, L= Isopropanol; for 2 RCOO= Benzoate, L= 2-Amino-4,6-dimethyl pyrimidine )] while 3 & 4 have the general formula, Cu₂(RCOO) ₄(S)₂ Cu₂(RCOO) ₄(L)₂ [RCOO=5-Chloro-thiophene-2-carboxylate L= 2-Amino-4,6-dimethyl pyrimidine, for 3 S= ethanol; for 4 S= methanol ]. A wide range of hydrogen bonds (of the O-H…O, N-H…O and N-H…N type) and π-π stacking interactions are present in the crystal structures.

Conclusions

All compounds contain the dinuclear units, in which two Cu (II) ions are bridged by four syn, syn-η¹:η¹:μ carboxylates, showing a paddle-wheel cage type with a distorted octahedral geometry. The compounds 1 & 2 contain a single dimeric unit while 3 & 4 contain two dimeric units. The structures 3 and 4 are very interesting co-crystals of two paddle wheel molecules. Also it is interesting to note that the compounds 3 & 4 are isostructural with similar cell parameters. Both the compounds 3 & 4 differ in the solvent molecule coordinated to copper in one of the dimeric units. In all the four compounds, each of the copper dimers has an inversion centre. Every copper has a distorted octahedral centre, formed by four oxygen atoms (from different carboxylate) in the equatorial sites. The two axial positions are occupied by copper and the corresponding ligand.

【 授权许可】

   
2013 Jenniefer and Muthiah; licensee Chemistry Central Ltd.

【 图 表 】

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Figure 12.

Scheme 1

【 参考文献 】

• [1]Sundberg MR, Uggla R, Melnik M: Comparison of the structural parameters in copper(II) acetate-type dimers containing distorted square pyramidal CuO4O and CuO4N chromophores. Polyhedron 1996, 15:1157-1163.
• [2]Cotton FA, Wilkinson G, Murillo CA, Bochmann M: Advanced Inorganic Chemistry. 6th edition. Singapore: John Wiley & Sons; 1999.
• [3]van Niekerk JN, Schoening FRL: A new type of copper complex as found in the crystal structure of cupric acetate, Cu2(CH3COO)4.2H2O. Acta Cryst 1953, 6:227-232.
• [4]Chadjistamatis I, Terzis A, Raptopoulou CP, Perlepes SP: First use of the succinamate(-1) ligand in 3d-metal chemistry: dinuclear copper(II) complexes with the rare [Cu2(η1:μ2-O2CR)2(η1:η1:μ2-O2CR)]+, [Cu2(η1:η1:μ2-O2CR)2]2+ and [Cu2(μ-OH)(μ-OH2)(η1:η1:μ2-O2CR)]2+ cores, and a novel one-dimensional polymerization of two different dimers (R=CH2CH2CONH2). Inorg Chem Commun 2003, 6:1365-1371.
• [5]Baranwal BP, Das SS, Singh P: Hydroxycarboxylato Complexes of Copper(II): Synthesis and Characterization. Synth React Inorg Met Org Chem 1998, 28:1689-1696.
• [6]Baran EJ, Etcheverry SB, Torre MH, Kremer E: Preparation and properties of copper(II) sebacate. Polyhedron 1994, 13:1859-1862.
• [7]Campbell GC, Haw JF: Determination of magnetic and structural properties in solids containing antiferromagnetically coupled metal centers using NMR methods. Magneto-structural correlations in anhydrous copper(II) n-butyrate. Inorg Chem 1988, 27:3706-3709.
• [8]Kawata T, Uekusa H, Ohba S, Furukawa T, Tokii T, Muto Y, Kato M: Magneto-structural correlation in dimeric copper(II) benzoates. Acta Cryst B 1992, 48:253-261.
• [9]Hull JW Jr, Romer DR, Podhorez DE, Ash ML, Brady CH: Development of potential manufacturing routes for substituted thiophenes – Preparation of halogenated 2-thiophenecarboxylic acid derivatives as building blocks for a new family of 2,6-dihaloaryl 1,2,4-triazole insecticides. Beilstein J Org Chem 2007, 3:23. BioMed Central Full Text
• [10]Sharma RC, Nagar R: Synthesis and antifungal properties of some transition metal complexes involving potentially active heterocyclic ligands. Croat Chem Acta 1988, 61:849-855.
• [11]Lumme P, Elo H, Janne J: Antitumor activity and metal complexes of the first transition series. Trans-bis(salicylaldoximato)copper(II) and related copper(II) complexes, a novel group of potential antitumor agents. Inorg Chim Acta 1984, 92:241-251.
• [12]Amphlett MJ, Callely AG: The degradation of 2-thiophenecarboxylic acid by a Flavobacterium species. J Biochem 1969, 112:12-13.
• [13]Gogoi BK, Bezbaruah RL: Microbial degradation of sulfur compounds present in coal and petroleum. Prog Ind Microbiol 2002, 36:427-456.
• [14]Hemamalini M, Muthiah PT, Butcher RJ, Lynch DE: The interplay of hydrogen-bonding and metal-coordination motifs in the formation of supramolecular patterns: Copper/zinc malonates–aminopyrimidine complexes. Inorg Chem Commun 2006, 9:1155-1160.
• [15]Buvaylo EA, Kokozay VN, Vassilyeva OY, Skelton BW, Jezierska J, Ozarowski A: A new Cu/Zn carboxylato-bridged 1D polymer: Direct synthesis, X-ray structure and magnetic properties. Inorganica Chimica Acta 2011, 373:27-31.
• [16]Marinho MV, Yoshida MI, Guedes KJ, Krambrock K, Bortoluzzi AJ, Hoerner M, Machado FC, Teles WM: Synthesis, Crystal Structure, and Spectroscopic Characterization of trans-Bis [(μ-1,3-bis(4-pyridyl)propane) (μ-(3-thiopheneacetate-O)) (3-thiopheneacetate-O)] dicopper(II), {[Cu2(O2CCH2C4H3S)4 μ-(BPP)2]}n: From a Dinuclear Paddle-Wheel Copper(II) Unit to a 2-D Coordination Polymer Involving Monatomic Carboxylate Bridge. Inorg Chem 2004, 43:1539-1544.
• [17]Lewis J, Linn C, Royston LK, Thompson RC: The chemistry of polynuclear compounds. Part III. Magnetic properties of some carboxylic acid derivatives of copper(II). J Chem Soc 1965, 6464-6477.
• [18]Morzyk-Ociepa B, Rozycka-Sokolowska E: Structures and spectroscopic studies of indolecarboxylic acids. Part III. Diamminetetrakis-μ-(O,O′-indole-3-carboxylate)dicopper(II). J Mol Str 2006, 78:69-77.
• [19]Morgan YR, Turner P, Kennedy BJ, Hambley TW, Lay PA, Biffin JR, Regtop HL, Warwick B: Preparation and characterization of dinuclear copper–indomethacin anti-inflammatory drugs. Inorg Chim Acta 2001, 324:150-161.
• [20]Barooah N, Karmakar A, Sarma RJ, Baruah JB: Self-assembly through hydrogen-bonding and C–H⋯π interactions in metal complexes of N-functionalised glycine. Inorg Chem Commun 2006, 9:1251-1254.
• [21]Sarma R, Karmakar A, Baruah JB: Synthesis and characterization of pyridine N-oxide complexes of manganese, copper and zinc. Inorg Chim Acta 2008, 361:2081-2086.
• [22]Deka K, Sarma RJ, Baruah JB: Nitrogen–oxygen bond formation during oxidative reactions of copper(II)benzoate complexes having 3,5-dimethylpyrazole. Inorg Chem Commun 2006, 9:931-934.
• [23]Dey SK, Bag B, Malik KMA, El Fallah MS, Ribas J, Mitra S: A Quasi-Tetrahedral Cu4 Cluster and a Helical-Chain Copper(II) Complex with Single Syn-Anti Carboxylate Bridges: Crystal Structure and Magnetic Properties. Inorg Chem 2003, 42:4029-4035.
• [24]Dey SK, Bag B, Zhou Z, Chan ASC, Mitra S: Synthesis, characterization and crystal structure of a monomeric and a macrocyclic copper (II) complex with a large cavity using benzylacetylacetone ligand. Inorg Chim Acta 2004, 357:1991-1996.
• [25]Saha MK, Dey DK, Samanta B, Edwards AJ, Clegg W, Mitra S: Synthesis, structure and magnetic properties of a mononuclear Cu(II) complex with a NNO donor Schiff base ligand and its oxalato- and oxamidato-bridged dinuclear complexes. J Chem Soc Dalton Trans 2003, 488-492.
• [26]Datta A, Choudhury CR, Talukder P, Mitra S, Dahlenburg L, Matsushita T: A novel doubly phenoxo-bridged Cu(II) trimer: synthesis, crystal structure and low-temperature magnetic behavior. J Chem Res 2003, 10:642-644.
• [27]Deacon GB, Phillips RJ: Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate. Coord Chem Rev 1980, 33:227-250.
• [28]Agterberg FPW, Provo Kluit HAJ, Driessen WL, Reedijk J, Oevering H, Buijs W, Veldman N, Lakin MT, Spek AL: Three dinuclear copper(II) carboxylates with the paddle-wheel cage structure as intermediates in copper(II) catalyzed oxidations of carboxylic acids. X-ray crystal structures of [tetrakis(diphenyl acetato-μ-O,O′)bis(acetonitrile-N)dicopper(II)] tetrakis(acetonitrile), [tetrakis(diphenyl acetato-μ-O,O′) bis(acetone-O)dicopper(II)] and [tetrakis(1-phenyl-1-carboxylato-μ-O,O′-cyclopentane)-bis(ethanol-O)dicopper(II)] bis (ethanol). Inorg Chim Acta 1998, 267:183-192.
• [29]Riggio I, van Albada GA, Mutikainen I, Turpeinen U, Reedijk J: Catena-Poly[[bis(nitrato)(pyrimidine)copper(II)] -[mu]-pyrimidine-N:N']. Acta Cryst C 2000, 56:380-381.
• [30]Yasui M, Ishikawa Y, Akiyama N, Ishida T, Nogami T, Iwasaki F: Dipyrimidine-copper(II) dinitrate complexes showing magnetic interactions. Acta Cryst B 2001, 57:288-295.
• [31]Bora SJ, Sarmah P, Phukan P, Das BK: Tetrakis([mu]-benzoato-[kappa]2O:O)bis{[4-(dimethylamino)pyridine-[kappa]N1]copper(II). Acta Cryst C 2007, 63:392-394.
• [32]Moncol J, Múdra M, Lönnecke P, Hewitt M, Valko M, Morris H, Švorec J, Melník M, Mazúr M, Koman M: Crystal structures and spectroscopic behavior of monomeric, dimeric and polymeric copper(II) chloroacetate adducts with isonicotinamide, N-methylnicotinamide and N, N-diethylnicotinamide. Inorg Chim Acta 2007, 360:3213-3225.
• [33]Selvakumar PM, Suresh E, Subramanian PS: New macrocyclic Cu(II)-bischelates with paddle wheel Cu2-acetate cage. Inorg Chim Acta 2008, 361:1503-1509.
• [34]Makhankova VG, BeCuischenko AO, Kokozay VN, Zubatyuk RI, Shishkin OV, Jezierska J, Ozarowski A: Direct Synthesis, Crystal Structures, High-Field EPR, and Magnetic Studies of Heterometallic Polymers Containing Manganese(II) Carboxylates Interconnected by [Cu(en)2]2+. Inorg Chem 2008, 47:4554-4559.
• [35]Moncol J, Kalinakova B, Svorec J, Kleinova M, Koman M, Hudecova D, Melnik M, Mazur M, Valko M: Spectral properties and bio-activity of copper(II) clofibriates, part III: crystal structure of Cu(clofibriate)2(2-pyridylmethanol)2, Cu(clofibriate)2(4-pyridylmethanol)2(H2O) dihydrate, and Cu2(clofibriate)4(N,N-diethylnicotinamide)2. Inorg Chim Acta 2004, 357:3211-3222.
• [36]Kozlevcar B, Radisek M, Jaglicic Z, Merzel F, Glazar L, Golobi A, Segedin P: Strong antiferromagnetism in the dinuclear 2-pyridone complex with N–C–O bridges: A paddle-wheel analogue of the dinuclear tetracarboxylates. Polyhedron 2007, 26:5414-5419.
• [37]Youngme S, Cheansirisomboon A, Danvirutai C, Pakawatchai C, Chaichit N, Engkagul C, van Albada GA, Costa JS, Reedijk J: Three New Polynuclear Tetracarboxylato-Bridged Copper(Ii) Complexes: Syntheses, X-Ray Structure and Magnetic Properties. Polyhedron 2008, 27:1875-1882.
• [38]Ma L, Lin W: Chirality-Controlled and Solvent-Templated Catenation Isomerism in Metal-Organic Frameworks. J Am Chem Soc 2008, 130:13834-13835.
• [39]Bruker : APEX2, SAINT and SADABS. Madison,Wisconsin, USA: Bruker AXS Inc; 2008.
• [40]Sheldrick GM: Acta Cryst A. 2008, 64:112.
• [41]Spek AL: Acta Cryst D. 2009, 65:148.
• [42]Farrugia LJ: POV-Ray - 3.5. Australia: Glasgow University; 2003.