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Dec 25, 2017 - J. C. Kim, H. Jo, A. J. Lough, J. Cho, U. Lee, S. Y. Pyun, Inorg Chem ... G. W. Frank Albert Cotton, Advanced inorganic chemistry, 6th ed.

JCBPS; Section A; November 2017 – January - 2018, Vol. 8, No. 1; 068-076.

E- ISSN: 2249 –1929

[DOI: 10.24214/jcbps.A.8.1.06876.]

Journal of Chemical, Biological and Physical Sciences An International Peer Review E-3 Journal of Sciences Available online Section A: Chemical Sciences


Research Article

Synthesis, Structural Characterization of Transition Metal Complex of an Oxydiacetic Acid Tuğba Aycan1*and Hümeyra Paşaoğlu1 Physics Department, Faculty of Art and Science, Ondokuz Mayıs University, Samsun, Turkey


Received: 27 November 2017; Revised: 16 December 2017; Accepted: 25 December 2017

Abstract: Compound based on the [Cu (oda)(hydet-en)] (oda=dianion of oxydiacetic acid, hydet-en=[N-(2-hydroxyethyl)-ethylenediamine]) has been synthesized and characterized by various spectroscopic methods (IR, UV-Vis, EPR) and thermal analysis (TG/DTG/DTA). Copper complex with mix ligands was determinated by single crystal Xray diffraction [oda]2- anion bridges Cu(II) ion with a bidentate coordination mode through its oxygen atoms of carboxylate groups. Single crystal X-ray data of the complex shows that the monomeric structure forms supramolecular frameworks with H-bonding. The FTIR investigation of the complex was performed within the mid-IR region, mainly focusing on the characteristic (COO)as and (COO)s stretching vibrations of oxydiacetic acid. The powder electron paramagnetic resonance spectra of Cu(II) complex at RT was recorded. The results of EPR and UV-Vis spectra agree with the X-ray diffraction data. Keywords: Oxydiacetic acid, [N-(2-hydroxyethyl)ethylenediamine], spectroscopy, UV-Visible spectroscopy, Thermal Analysis.


INTRODUCTION The construction of supramolecular architectures has been attractive to a quite attention due to their potential applications in magnetism, sensors, porous, catalysis, optics, molecular recognition 1-7. Polycarboxylic acids interesting structural properties can be summarized as follows: (i) Carboxylic groups of polycarboxylic acids are widely used because they are easily deprotonated. (ii) The polycarboxylic acids are both hydrogen bond donors and acceptors due to the presence of the COOH and the COO- groups, increasing the possibilities of intermolecular hydrogen bonding interaction to form higher dimensional 68

J. Chem. Bio. Phy. Sci. Sec. A, November 2017 – January - 2018, Vol. 8, No. 1; 068-076. DOI:10.24214/jcbps.A.8.1.06876.]

Synthesis …

Tuğba and Hümeyra.

. networks 8-13. The oxydiacetate dianion [oda]2- exhibits a versatile ligand behavior as bound one or more metal ions as either monodentate or chelate. The oxydiacetic acid has diverse coordination modes with the available donor sites which is two each of the two carboxylate group and one of the ether group 14. In this study, oxydiacetic acid (oda: -O2C–CH2–O–CH2–CO2-) was selected from family of aliphatic polycarboxylic acids. Using its doubly deprotonated form (oda), [Cu(oda)(hydet-en)] was synthesized by conventional methods. The structural properties of the complex were characterized by single crystal X-ray diffraction technique, FT-IR, UV-Vis, EPR spectroscopy and thermal analysis. MATERIAL AND METHODS Synthesis of [Cu(oda)(hydet-en)]: A solution of H2oda (5 mmol, 0.67 g) in water was slowly added to the solution of NaOH (5 mmol, 0.2 g) with stirring. Then, the solution of copper (II) sulphate pentahydrate (5 mmol, 1.25 g) was drop wise. The blue mixture was filtered and left for crystallization. The resulting blue crystals (1 mmol, 0.38 g) were solved in water and added to a water solution of hydet-en (1 mmol, 0.1 g). The final solution was heated and stirred for an hour. The filtered solution was left for crystallization at ambient temperature. Blue single crystals of the complex were obtained after two weeks. Materials and Instrumentation: All chemical materials were purchased from commercial companies and used without further purification. The FT-IR spectra with using KBr pellets were recorded in a Bruker Vertex 80V FT-IR spectrometer in the mid-IR region (4000-400 cm-1). The spectra was converted in to transmittance using Bruker OPUS software. A TG8110 thermal analyzer was used to record simultaneous TG, DTG and DTA curves in nitrogen atmosphere at a heating rate of 10 K min−1 in the temperature range 30–1000 °C using platinum pats. The electron spin resonance spectra was recorded using a JEOL JESFA300 model X-band spectrometer. The magnetic field modulation frequency was 100 kHz and the microwave power was around 0.998 mW. The UV-Visible spectra of title compound was recorded at room temperature in aqua solution on a Bio-crom 8500 II spectrophotometer working between 200 and 1100 nm. The absorption spectra of title complex was drawn using VISION collect Software. XRD data was collected using a Stoe IPDS diffractometer at 296 K by graphite monochromatic Mo Kα radiation (λ=0.71073 Å). The crystal structure was analyzed by direct methods and all non-hydrogen atoms were refined anisotropically by full matrix least-squares methods using the program SHELX9715. WinGX 16, ORTEP-3 for Windows17 and MERCURY 18 software were used for molecular drawings and other materials. RESULTS AND DISCUSSION Crystal and Molecular Structure of the Complex [Cu(oda)(hydet-en)]: As shown in Figure. 1a, the title compound is a monomer that Cu(II) ion is coordinated to a tridentate chelating oxydiacetate dianion (fac configuration)19 and hydet-en ligand. The geometric values describing the coordination polyhedron of Cu(II) ion correspond to a distorted octahedral environment. While the equatorial position is occupied by the oxygen atoms of the oda2- ion and by the nitrogen atoms of hydet-en ligand, the axial positions are occupied by the remaining oxygen atom of the hydet-en ligand and by the ether atom. As shown in Table 1a, the bond lengths Cu-O1 (2.278(2) Å) and Cu-O3 (2.452 (2) Å) are longer than the others resulting in a distorted octahedral geometry, is known Jahn-Teller distortion. Selected geometric parameters of the complex together with those of, [Cu(oda)(1,10-phen)]. 3H2O19 and [Cu(Hydet-en)(ox)]20 are comparatively given in Table 1a. In the crystal packing of the complex, the amide group of hydet-en ligand connects monomers by involving in N1–H1∙∙∙O6i (i: -x+2, y-1/2, -z+3/2) hydrogen bond with the carboxylate group


J. Chem. Bio. Phy. Sci. Sec. A, November 2017 – January - 2018, Vol. 8, No. 1; 068-076. DOI:10.24214/jcbps.A.8.1.06876.]

Synthesis …

Tuğba and Hümeyra.

. of oda2- (Table 2a). This is resulted in a linear 1D chain of rings along [010]. More specifically, the coordination monomers are connected by C(6) chains (Figure 1b). In addition, these H-bonded chains are interconnected by N2-H2B∙∙∙O4iii (iii: -x+1, -y+1, -z+1) H-bond formed by DA:AD type organization of hydet-en (N2) and [oda]2- (O4) ligands resulting in 𝑅22(8) synthons at ( ½-n, ½ , ½; n=0 or integer) positions and by N2-H2A∙∙∙O5ii (ii: x-1, y, z) H-bonds resulting in 𝑅44(16) synthons at (1-n, ½ ,½; n=0 or integer) positions. Thus, a 2D supramolecular sheet is constructed (Figure 1c). O atoms of hydet-en and oda2connect 2D H-bond polymer sheets in by involving in O1-H2∙∙∙O2iv (iv:-x+2, -y+1, -z+1) (Table 1b). The coordination polymers are connected by 𝑅22(8) synthons centered at (1/2, n-1/2, 1/2; n=0 or integer). Thus, a 3D supramolecular structure is formed (Figure 1d).

Figure 1a: The molecular structure of the complex, with drawn with 20% displacement ellipsoids

Figure 1b: Connection of coordination monomers by N2–H2∙∙∙O2 (x+1, y−1/2, −z+3/2) H-bond in a complementary way. Non-relevant H atoms were omitted for clarity.


J. Chem. Bio. Phy. Sci. Sec. A, November 2017 – January - 2018, Vol. 8, No. 1; 068-076. DOI:10.24214/jcbps.A.8.1.06876.]

Synthesis …

Tuğba and Hümeyra.

. Table 1a: Selected bond distances (Å) and bond angles (º) for the title complex and some similar structures. complex

Bond distance Cu(oda)19


Bond Angle


Cu-N1 Cu-N2 Cu-O1 Cu-O2 Cu-O4 Cu-O3 C5-O2 C5-O5 C8-O4

2.019(2) 2.000(2) 2.278(2) 1.995(2) 1.960(2) 2.452(2) 1.273(3) 1.223(3) 1.261(3)

N1–Cu-N2 O1–Cu–N1 O1–Cu–O2 O1-Cu–N2 O1-Cu-O4 O4-Cu-O2 O4-Cu-N1 O4-Cu-N2 O2-Cu-N1 O4-Cu-O3 O2-Cu-O3

84.93(9) 79.06(9) 92.28(8) 104.09(10) 88.60(8) 91.31(7) 167.39(9) 95.64(9) 91.81(8) 76.60(2) 75.64(3)


1.977(3) 1.937(4) 2.488(3) 1.265(6) 1.234(6) 1.260(6)

76.37(14) 73.87(12)

Figure 1c: The 2D structure of the complex in (201) plane constructed by the connection through adjacent sheets. Non-relevant H atoms were omitted for clarity. Symmetry codes are as given in Table 1b.


J. Chem. Bio. Phy. Sci. Sec. A, November 2017 – January - 2018, Vol. 8, No. 1; 068-076. DOI:10.24214/jcbps.A.8.1.06876.]

Synthesis …

Tuğba and Hümeyra.

. Table 1b: Hydrogen bond geometry (Å,º) for the complex D−H···A


d(H···A) d(D···A)