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The Tetra–µ–[N-phenylanthranilato](O,O’)–bis[(2-amino-4-methyl)pyridine Copper(II)] Complex CrystalMurat Taş a , Abdullah Titiz a , Elif Karabağ a , Mukadder Kaya a , Mehmet Ataseven a &

Hakan Dal ba Giresun University, Art and Sciences Faculty, Department of Chemistry , Giresun , Turkeyb Anadolu University, Sciences Faculty, Department of Chemistry , Eskişehir , TurkeyAccepted author version posted online: 17 Apr 2013.Published online: 14 May 2013.

To cite this article: Murat Taş , Abdullah Titiz , Elif Karabağ , Mukadder Kaya , Mehmet Ataseven & Hakan Dal (2013) TheTetra–µ–[N-phenylanthranilato](O,O’)–bis[(2-amino-4-methyl)pyridine Copper(II)] Complex Crystal, Synthesis and Reactivity inInorganic, Metal-Organic, and Nano-Metal Chemistry, 43:9, 1212-1223, DOI: 10.1080/15533174.2012.757237

To link to this article: http://dx.doi.org/10.1080/15533174.2012.757237

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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1212–1223, 2013Copyright C© Taylor & Francis Group, LLCISSN: 1553-3174 print / 1553-3182 onlineDOI: 10.1080/15533174.2012.757237

The Tetra–μ–[N-phenylanthranilato](O,O’)–bis[(2-amino-4-methyl)pyridine Copper(II)] Complex Crystal

Murat Tas,1 Abdullah Titiz,1 Elif Karabag,1 Mukadder Kaya,1 Mehmet Ataseven,1

and Hakan Dal2

1Giresun University, Art and Sciences Faculty, Department of Chemistry, Giresun, Turkey2Anadolu University, Sciences Faculty, Department of Chemistry, Eskisehir, Turkey

Tetra–μ–[N-phenylanthranilato](O,O′)–bis[2-amino-4-methyl)pyridine copper(II)] (bisdichloromethane solvate and unsolvate)in one crystalline contains two independent binuclears, one ofwhich is unsolvate and the other one is dichloromethane solvate.The phenyl ring planes in the asymmetric units were not parallel toeach other [44.47(14)◦ and 52.50(13)◦ for unsolvate unit, 53.30(14)◦and 49.59(13)◦ for solvate unit] and the distance between the twocenters of phenyl rings was measured as 5.064 Å (for Cg2-Cg3),5.005 Å (for Cg4-Cg5), 5.048 Å (for Cg7-Cg8), and 5.088 Å (forCg9-Cg10) for NPA ligands. The complex molecules showed threedimensional supramolecular networks by O–H···O, C–H···O,C–H···π , and π···π interactions.

Keywords amino acids, binuclear copper complex, carboxylate lig-ands, O donor ligands, π interactions

INTRODUCTIONN-phenylanthranilic acid (NPA; i.e., 2–[N–phenylamino]

benzoic acid) is a phenyl derivative of anthranilic acid which isboth an almost ubiquitous constituent of biological systems anda metabolic precursor of important amino acids such as trypto-phan and also a component of humic acids and serves as a usefulmodel for the coordination chemistry of complex biopolymer.[1]

Some N-phenylanthranilic acids are known as nonsteroidal anti-inflammatory drugs (NSAIDs) such as, diclofenac, mefenamic,and tolfenamic acids and N-phenylanthranilic acids are also po-tent against AKR1C and COX isozymes.[2–4]

NPA is also used as indicator for titrations in some analyticalapplications and its some complexes show catalitic and lumi-nescent activities.[5–14] N–phenylanthranilic acid is also widelyused in medicine, pharmacy, analytical chemistry, and organicchemistry as starting material for the synthesis of biologicallyactive compounds, comparative medical research, and metal iondetermination.[15]

Received 21 November 2012; accepted 5 December 2012.Address correspondence to Murat Tas, Giresun University, Art and

Sciences Faculty, Department of Chemistry, Giresun, Turkey. E-mail:murat.tas@giresun.edu.tr.

In addition, a number of magnetically interacting dinuclearcopper(II) complexes have been shown to be catalytic activityin the oxidation processes.[16] Dinuclear copper and iron com-plexes, especially, are widely studied for mimicking the bimetal-lic sites in various enzymes.[17] Studies on binuclear metal com-plexes have contributed to a better knowledge of oxygen trans-port and activation by metalloenzymes such as heamocyanin andtyrosinase (Cu2) and some industrial catalytic processes.[16]

The aim of the present work is the synthesis and charac-terization of novel N–phenylanthranilic acid complexes withcopper(II) ion.

EXPERIMENTAL

Materials and MeasurementsOnly commercially available reagent grade chemicals were

used. FT-IR spectra (4000–450 cm–1) were recorded on a Perkin-Elmer Spectrum 100 FT-IR spectrophotometer (Giresun Univer-sity, Turkey) with samples prepared as KBr pellets. Magneticsusceptibility was measured using a Sherwood Scientific MX1Gouy Magnetic Balance (Giresun University, Turkey) at roomtemperature. UV–vis spectra was recorded with a PG–T80+UV–vis spectrometer (PG Instruments, Giresun University,Turkey). A SII-O Extar 6000 thermal analyzer (SII Nanotech-nology Inc., Giresun University, Turkey) was used to recordTG, DTG, and DTA curves in static air atmosphere at a heatingrate of 10 Kmin–1 from 30 to 700◦C using platinum crucibles.Highly sintered α–Al2O3 was used as a reference. Elementalanalysis for C, H, and N were performed using a Costech ECS4010 CHNSO analyzer (Giresun University, Turkey).

Preparation of the ComplexN-phenylanthranilic acid (1.065 g, 0.005 mol) was dissolved

in 20 mL ethanol and heated to 50◦C. To the solution copperpowder (0.318 g, 0.005 mol) was added. After 1 h 2-amino-4-methylpyridine (0.520 g, 0.005 mol) was directly added tothe mixture and stirred for 2 h at 50◦C. The color of the mix-ture changed from dark green to brown. To the mixture 20 mLdichloromethane was added at room temperature and stirred for

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5 minutes and filtered. And then to decrease the polarity ofthe mixture, 20 mL n-hexane slowly added to the solution. Abrown crystalline compound was obtained from the solution byslow evaporation for several days. Yield: 85% (based on NPA).Anal. Calcd. for C65H58Cl2Cu2N8O8 (%): C, 61.13; H, 4.58; N,8.77. Found: C, 61.22; H, 4.40; N, 9.01. IR data (KBr, cm−1):3468(m), 3367 (m), 3327 (s), 3314 (s), 1629 (s), 1454 (m), 1320(m), (m), 1270 (s).

Crystallographic AnalysisBruker Smart Apex CCD diffractometer (Anadolu Univer-

sity, Turkey) mounted Mo-Kα X-ray source was used for diffrac-tion experiment at 293(2) K. The structure was solved by di-rect methods and refined by using SIR2004 and SHELXL-97, respectively.[18,19] All non-hydrogen atoms were refinedanisotropically by full-matrix least-squares methods (SHELXL-97).[19] The hydrogen atoms were placed in geometrically ide-alized positions (except amine hydrogens) and refined as riding

TABLE 1Crystal data and structure refinement for the compound

Crystal Data NFA2A4MPy

Formula (C64 H56 Cu2 N8 O8), CH2Cl2

Formula weight 1277.19Crystal system TriclinicSpace group P–1a, b, c [Å] 11.120(2), 12.397(3),

22.764(3)α, β, γ [◦] 94.880(7), 97.200(7),

110.780(7)V [Å3] 2882.328Z 2dcalc [g/cm3] 1.472μ(MoKα) [mm–1] 0.896F(000) 1320Crystal size [mm] 0.094 × 0.211 × 0.527Data collectionTemperature (K) 293Radiation [Å] MoKα (0.71073)Theta min-max [◦] 1.8, 28.4Dataset –14→10; –16→16; –30→ 0Tot., unique data, R(int) 98782, 14294, 0.033Observed data [I > 2σ (I)] 11779RefinementNref, Npar 14294, 774R, wR2, S 0.0467, 0.1165, 1.05Max. and Av. shift/error 0.00, 0.00Min. and Max. resd. dens.

[e/Å3]–1.03, 0.89

model. Software programs were used; for data collection, BrukerSADABS[20]; for data reduction, Bruker SAINT v7.53A[20]; formolecular graphics, Mercury-2.0[21]; to prepare the material forpublication, WinGX.[22]

RESULTS AND DISCUSSION

Crystal Structure Description of the ComplexExperimental data are listed in Table 1. Selected bond lengths

and angles and hydrogen-bond geometry are given in Tables 2and 3, respectively.

The compound contains two different complex units. One ofthem is solvate free and the other one has two dichloromethanesolvate molecules (Figure 1). In both complex units, the twoCu(II) ions are 2.643(1) and 2.661(1) Å apart and are bridgedby the carboxylate groups of four N–phenylanthranilate (NPA)ligands. Each Cu(II) atom is coordinated equatorially by fourNPA O-atoms (Cu–O: 1.960, 1.979, 1.983, and 1.972 Å for un-solvate unit and Cu–O: 1.991, 1.950, 1.982, and 1.971 Å forsolvate units) and apically to the 2-amino-4-methyl-pyridine(AMPy) N-atoms (Cu–N: 2.165 and 2.166 Å for solvate and un-solvate unit, respectively) (Figures 1–3, Table 2). The unsolvateand solvate units locate on crystallographic centers as to eachother by a 53.36◦ clockwise rotation (Figure 1).

To describe the geometry around the metal ions, the structuralindex parameters τ that τ = α–β/60◦, where α and β are thetwo largest angles (α > β) were calculated. The synthesizedcomplexes have τ values of 0.0 [τ = (168.11 – 168.02)/60 =0.002 and τ = (167.22 – 166.62)/60 = 0.010], indicating squarepyramidal geometries around copper(II) ions in both complexunits.

All the ligands around the Cu(II) centers in the complexesare arranged in a trans configuration (Figures 1–3). The planeof phenyl rings which bonding to the carboxylate groups in thecomplex units nearly lay on a plane forming by four coordinatedoxygen atoms.

The phenyl rings of NPA ligands in both complex units, werenearly planar with the largest deviation from the plane being thatof atoms C2 [–0.024(3)] for Cg2; C8 [–0.010(3)] for Cg3; C15[0.010(3)] for Cg4; C21 and C24; [–0.014(3)] for Cg5; andC27 [–0.024(3) Å] for pyridine rings (Cg1) in unsolvate unit(Figure 2), that of atoms C34 [–0.012(3)] for Cg7; C44[–0.008(4)] for Cg8; C47 [0.009(3)] for Cg9; C54 [–0.009(3)]for Cg10; and C60 [–0.017(3) Å] for pyridine rings (Cg6)in solvate unit (Figure 3). The phenyl ring planes in theasymmetric units were not parallel to each other [44.47(14)◦

and 52.50(13)◦ for unsolvate unit, 53.30(14)◦ and 49.59(13)◦

for solvate unit] and the distance between the two cen-ters of phenyl rings was measured as 5.064 Å (for Cg2-Cg3), 5.005 Å (for Cg4-Cg5), 5.048 Å (for Cg7-Cg8), and5.088 Å (for Cg9-Cg10) for NPA ligands. So, these re-sults indicating that the handled crystal had two isomeric

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TABLE 2Selected bond length (Å) and angle (◦) for complex units

Unsolvate unit Solvate unit Bisethanol complexa

Bond Length Bond Length Bond Length

Cu1–Cu1ii 2.6426(5) Cu2–Cu2i 2.6635(5) Cu1–Cu1 2.591(2)Cu1–O1 1.9602(18) Cu2–O5 1.9500(19) Cu1–O1 1.954(7)Cu1–O2 1.9717(17) Cu2–O6 1.9913(16) Cu1–O2 1.960(7)Cu1–O3 1.9787(18) Cu2–O7 1.9713(18) Cu1–O3 1.962(9)Cu1–O4 1.9833(19) Cu2–O8 1.9821(18) Cu1–O4 1.981(9)Cu1–N3 2.165(2) Cu2–N7 2.166(2) Cu1–Oethanol 2.131(7)O1–C1 1.260(3) O5–C33 1.260(4) O1–C1 1.250(11)O2–C1ii 1.271(3) O6–C33i 1.274(4) O2–C1i 1.278(11)O3–C14 1.267(3) O7–C46 1.266(3) O3–C14i 1.260(10)O4–C14ii 1.267(3) O8–C46i 1.267(3) O4–C14 1.255(13)N1–C7 1.373(4) N5–C35 1.376(4) N1–C7 1.372(12)N1–C8 1.403(4) N5–C40 1.413(4) N1–C8 1.392(12)N2–C20 1.383(4) N6–C52 1.375(3) N2–C20 1.385(14)N2–C21 1.414(4) N6–C53 1.404(3) N2–C21 1.396(11)N3–C27 1.344(3) N7–C59 1.345(4)N3–C31 1.349(3) N7–C63 1.356(3)N4–C27 1.369(3) N8–C59 1.353(4)N4–H4B 0.880(2) C61-C64 1.506(4)C29-C32 1.502(3) C65-Cl2 1.805(4)

Bond Angle Bond Angle Bond Angle

O1–Cu1–O2i 168.02(7) O5–Cu2–O6ii 166.62(8) O1–Cu–O2 168.9(3)O2i–Cu1–O3 87.79(8) O6ii–Cu2–O8ii 86.98(8) O1–Cu–O3 88.9(3)O2i–Cu1–O4i 89.60(8) O6ii–Cu2–O7 93.26(8) O1–Cu–O4 89.5(3)O1–Cu1–N3 93.23(8) O5–Cu2–N7 97.14(8) O1–Cu–Oethanol 99.0(3)O3–Cu1–N3 97.41(8) O8ii–Cu2–N7 96.62(8) O2–Cu–O3 89.2(3)O1–Cu1–O3 91.79(8) O5–Cu2–O8ii 88.45(8) O2–Cu–O4 90.2(3)O1–Cu1–O4i 88.37(8) O5–Cu2–O7 88.45(8) O2–Cu–Oethanol 92.0(3)O3–Cu1–O4i 168.11(7) O8ii–Cu2–O7 167.22(7) O3–Cu–O4 169.1(3)O2i–Cu1–N3 98.69(7) O6ii–Cu2–N7 95.88(8) O3–Cu–O5 93.8(3)O4i–Cu1–N3 94.45(8) O7–Cu2–N7 96.07(8) O4–Cu–Oethanol 97.1(3)

i = –x, 1–y, –z, ii = –x, –y + 1, –z + 1.aTetra–μ–[2–(phenylamino) benzoato](O,O′)–bis[ethanol copper(II)].[23]

forms of tetra–μ–[N-phenylanthranilato](O,O′)–bis[(2-amino-4-methyl)pyridine copper(II)]. The similar isomerism in thesame crystal lattice was reported previously.[23–25]

The Cu(II)···Cu(II) separations (between 2.64 and 2.66Å) in the synthesized compound were longer than tetra-μ-[N-phenylanthranilato](O,O′)-bis[(ethanol)copper(II)] com-plex [(2.591(2) Å] may attributed to steric hindrance of the2-amino-4-methylpyridine (Table 2).[26]

The Cu(II)–N distances [∼2.1 Å)] in the synthesizedcompound were also similar with the reported other com-

parable structures, Cu(II)–NPy [2.147(2) and 2,165(2) Å],or Cu(II)–NPh-Py [2.150(3) Å], in tetra–μ–methacrylato–bis[pyridine copper(II)] and tetra–μ–acetato–bis[4-pheny-lpyridine copper(II)] complexes, respectively.[27,28]

The amine hydrogen atoms of the NPA ligands in both com-plex units formed intramolecular hydrogen bonds with the oxy-gen atoms of NPA ligands (Figures 2 and 3).

In the unsolvate unit, the N1 atom of the NPA ligands also,formed hydrogen bonds showing bifurcated hydrogen bondstype, with the amine nitrogen atoms of AMPy ligands (Figure 2).

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TABLE 3Interactions of the compound in the solid state

H Bond geometry

D–H···A D–H H···A D···A D–H···AN4–H4A···O2 0.891(2) 2.6072(18) 3.069(3) 113.18(17)N4–H4A···O3 0.891(2) 2.2800(18) 3.110(3) 155.02(15)N8–H8A···O5 0.884(2) 2.8803(19) 3.343(3) 114.29(17)N8–H8A···O7 0.884(2) 2.0965(18) 2.889(3) 148.85(16)C48–H48···N8 0.93 2.91 3.692(4) 143.0C51–H51···N4 0.93 2.99 3.769(3) 142.9C58–H58···Cl2 0.93 3.04 3.704(3) 129.6N1–H1···N4i 0.917(2) 2.660(3) 3.363(3) 134.09(15)N1–H1···O2i 0.917(2) 1.9321(17) 2.670(3) 136.07(15)N2–H2···O4i 0.871(2) 1.9618(17) 2.664(3) 136.76(15)N5–H5···O6ii 0.885(2) 1.9618(18) 2.650(3) 133.56(16)N6–H6···O8ii 0.898(2) 1.9700(17) 2.647(3) 130.99(15)C32–H32B···O1iii 0.96 2.57 3.523(3) 171.6C32–H32B···O3iii 0.96 3.06 3.564(3) 114.2C64–H64C···O7iv 0.96 2.70 3.349(3) 125.5C60–H60···N5v 0.93 2.85 3.741(3) 161.0C64–H64C···O6v 0.96 2.46 3.389(3) 163.3C10–H10···O5viii 0.93 2.90 3.788(4) 161.2

X-(H or Cl)···π InteractionsC65–H65A···Cg9 0.97 2.54 3.4654) 158C65–Cl1···Cg7 1.727(4) 3.4386(16) 4.474(4) 116.00(15)C65–Cl1···Cg9 1.727(4) 3.9906(14) 3.465(4) 59.96(12)N4–H4B···Cg10iii 0.8800 2.63 3.3913) 145N8–H8B···Cg8v 0.8500 2.78 3.6093) 163C23–H23···Cg4vi 0.93 2.98 3.6633) 131C41–H41···Cg7vii 0.93 2.82 3.6053) 143

π ··π InteractionsCg(1)···Cg(1)iii 3.7590(15) 0a

Cg(6)···Cg(6)iv 3.6190(15) 0a

i = –x, –y + 1, –z + 1ii = –x, –y + 1, –ziii = –x + 1, –y + 1, –z + 1iv = –x – 1, –y + 1, –zv = x – 1, y, zvi = –x + 2, –y + –z + 1vii = –x + 1, –y + 2, –zviii = x, y, z + 1Cg refer to center of the phenyl or pyridine ringCg1 = N3–C27–C28–C29–C30–C31Cg4 = C15–C16–C17–C18–C19–C20Cg6 = N7–C59–C60–C61–C62–C63Cg7 = C34–C35–C36–C37–C38–C39Cg8 = C40–C41–C42–C43–C44–C45Cg9 = C47–C48–C49–C50–C51–C52Cg10 = C53–C54–C55–C56–C57–C58aThe angle between the aromatic ring planes

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FIG. 1. A view of the compound. Ellipsoids are drawn at 50% probability level and interactions are shown by broken lines. The intramolecular interactions andsome hydrogen atoms were omitted for clarity. (Symmetry code, i = –x, 1 – y, 1 – z, ii = –x, 1 – y, –z.) (color figure available online).

The amine hydrogen atoms of AMPy ligands also formed bi-furcated hydrogen bonds with the nearest oxygen atoms of theNPA ligands (Figure 2, Table 3).

In the solvate unit, the nitrogen atoms of the NPA ligands onlyformed common hydrogen bonds. As a different from unsolvateunit, an amine hydrogen atoms of AMPy ligands formed three-centered hydrogen bonds with the nearest oxygen atoms of theNPA ligands and a chlorine atoms of dichloromethane solvatemolecules (Figure 3). Also, the C58 atom of a phenyl groupof NPA ligand acts as hydrogen bond donor by using its hy-drogen atom to Cl2 atom of dichloromethane solvate molecule(Figure 3). In addition to these, the Cl1 atom dichloromethaneformed Cl···π interactions with the center of a phenyl ring (Cg7and Cg9), which bonded to carboxylate group of NPA ligandsand the carbon atom of dichloromethane, formed a C-H···πinteraction with nearest center of phenyl ring (Cg9) of NPAligands (Figure 3, Table 3).

So, the dichloromethane strongly located between the twoNPA ligands in the asymmetric unit to form dichloromethanesolvate unit (Figures 1 and 3).

The C10 atom of unsolvate complex unit at –x, 1 – y, 1 – z,formed hydrogen bond with the O5 atom of NPA ligand of sol-vate unit at –x, 1 – y, –z and also the NH2 group of AMPy ligandof unsolvate complex unit showed an interaction with the center

of a phenyl ring of NPA ligand of solvate unit. The solvate unitformed hydrogen bonds by using a hydrogen atom of a phenylgroup of NPA ligand with the amine nitrogen atom of AMPyligand of unsolvate complex. So forming the C10i–H10···O5ii,C51–H51···N4, and N4–H4B···Cg10 interactions bonded to sol-vate and unsolvate complex unit to each other along and the boththe complex units extended along the c-axis by these interactions(Figures 4–6).

By using their one of the hydrogen atoms, the methyl groupsof AMPy ligands of the complex units acted as bifurcated hy-drogen bond donor to oxygen atoms of NPA ligands (O1iii andO3iii atoms for unsolvate units and O6iv and O7iv atoms forsolvate unit) to extend and to form an infinite polymeric chainalong the a-axis. Also the pyridine rings of both complex unitscomposed π ···π stacking interactions with the nearest complexunits at this direction (Figure 4). As a different from unsolvateunit, in polymeric chains of the solvate units, contributing toform polymeric chain, the C60 atom of AMPy and amine group(N8) also formed hydrogen bond, with the N5v atom and a ringcenter of a phenyl ring (Cg6v) of a NPA ligand, respectively, atx – 1, y, z (Figure 4).

The each complex units extend to form an infinite polymericchain along the b-axis by the C23–H23···Cg4vi (vi = –x + 2,–y + 1, –z + 1) and C41–H41···Cg7vii (vii = –x + 1, –y + 2, –z)

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FIG. 2. A view of the unsolvate unit of the compound showing the crystallographic labeling and intramolecular interactions. Ellipsoids are drawn at 50%probability level and interactions are shown by broken lines. (Symmetry code, i = –x, 1 – y, 1 – z) (color figure available online).

interactions formed an infinite polymeric chain of complex unitsalong the b-axis for solvate and unsolvate unit, respectively. Sothe both complex units showed independent two-dimensionalnetworks along the a- and b-axis (Figure 5).

The independent two dimensional solvate and unsol-vate networks bonded to each others by C10–H10···O5viii,C51–H51···N4, and N4–H4B···Cg10 interactions which wereexplained previously, along the c-axis to form three dimensionalsupramolecular networks (Figure 6).

IR, UV–Vis Spectroscopies, and Magnetic MomentMeasurement

The IR spectrum of N–phenylanthranilic acid shows peaks at3332, 1658, 1436, 1324, and 1260 cm–1, which were attributed

to N–H, C=O+COO–asym–vib., COO–

sym–vib., COO–asym–strech., and

–C–N– vibrations, respectively.[18] The O–H bands of the freeligand at 2860, 2732, 2640, and 2564 cm–1 disappear in thespectra of complexes and indicate that the carboxylic acidproton is removed to form the N–phenylanthranilate anionon complexation.[16,18] The N–H peak for N–phenylanthranilicacid occurs at 3367 cm–1 for the compound and indicatesthat the N–H proton is not removed on complexation.[26,29]

The closed two peaks at 3327 and 3314 cm–1 were attributedto the NH2 vibration of AMPy ligands. Also, the peak at3468 was attributed to dichloromethane molecules in solvateunit.

The difference between the asymmetric (νasym) and sym-metric (νsym) carboxylate vibrations ( = νasym−νsym) is often

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FIG. 3. A view of the dichloromethane solvate unit of the compound, showing the crystallographic labeling and intramolecular interactions. Ellipsoids are drawnat 50% probability level and interactions are shown by broken lines. (Symmetry code, ii = –x, 1 – y, –z.) (color figure available online).

used to determine the coordination modes of the carboxylategroup. The peaks assigned to COO–

asym, COO–sym. vibrations are

shifted to 1629, 1454 cm–1 ( = 175), relative to the free lig-and, indicating that the carboxylate group participates in thecoordination with the metal ions by deprotonation in bridgingmode.[26,30–33]

The room temperature magnetic moment was measured as1.46 BM indicating antiferromagnetic coupling between the twoCu(II) centers.

The UV–Vis spectra of an ethanol solution of the compoundshowed two bands at 685 nm (ε = 170 Lcm–1mol–1) and at750 nm (ε = 200 Lcm–1mol–1), respectively. These are con-sistent with a square pyramidal environment for a d9 electronconfiguration.

Thermal AnalysesThe compound undergoes complete endothermic decomposi-

tions in four stages (Figure 7). The first stage occurs at 90–130◦C(DTAmax.: 115◦C) and corresponds to an endothermal removalof two dichloromethane solvate molecules (calcd.: 6.6%, found:6.3%). It is not easy to explain reasonably without Mass spectraof evolution fragments during thermal decomposition for otherdecomposition stages. The second stage, between 130◦C and181◦C is accompanied by a 5.9% mass-loss (DTAmax.: 154◦C).In the third stage of pyrolysis (181–285◦C), the organic residuewas lost 37.7% mass (DTAmax., 257◦C). The fourth stage, be-tween 285◦C and 525◦C, is accompanied by a 36.6% mass-loss (DTAmax.: 393◦C). But it can be said that a total of 82.5%(final product = 17.5%) of the original mass of compound was

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FIG. 4. A view of the compound along a–c-axis. The intramolecular interactions and some hydrogen atoms and solvate molecules were omitted for clarity (colorfigure available online).

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FIG. 5. A view of the compound along b–c-axis. The intramolecular interactions and some hydrogen atoms and solvate molecules were omitted for clarity.(Symmetry code, ii = –x, 1 – y, –z.) (color figure available online).

removed between the 30 and 525◦C. The calculated final massesare 10%, 11.2%, 12.5%, and 17.4% for metallic Cu, Cu2O,CuO, and Cu3O2, respectively. These results may indicate toform Cu3O2 as a final product. But, the formation of Cu3O2 pre-viously reported at low temperature (between 110 and 200◦C)and low oxygen pressure.[34] The exothermal DTA peak at 200◦Cmay indicate forming of Cu3O2 but is not easy to say in theseexperimental conditions. So, the final product forming at hightemperature may be an aggregate of Cu2O+CuO (calcd. 17.4%),which is consistent with the characterized structure (Figure 1).

CONCLUSIONSThe complex, tetra–μ–[N-phenylanthranilato](O,O′)–bis[2-

amino-4-methyl)pyridine copper(II)] was synthesized by thereaction of N–phenylanthranilic acid and copper powderpresence of 2-amino-4-methyl)pyridine and crystallized fromethanol-dichloromethane-n-hexane mixture (1:1:1). The crys-tal structure of the compound contains two independent bin-uclear which one of them is unsolvate and the other onedichloromethane solvate, cage complexes and each dimer lo-cate on a crystallographic inversion centre (triclinic, P–1 space

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N-PHENYLANTHRANILATO 1221

FIG. 6. A view of packing diagram of the compound (color figure available online).

FIG. 7. Thermal analysis curves of the compound.

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1222 M. TAS ET AL.

group). According to the phenyl ring planes the distancebetween the two centers of phenyl rings of NPA ligands,bond lengths and angles, the handled crystal has two iso-meric forms of tetra–μ–[N-phenylanthranilato](O,O′)–bis[(2-amino-4-methyl)pyridine copper(II)]. The complex moleculesshow three-dimensional supramolecular networks by O–H···O,C–H···O, C–H···π , and π ···π interactions.

SUPPLEMENTARY MATERIALSCrystallographic data (excluding structure factors) have been

deposited with the Cambridge Crystallographic Data Centre asthe supplementary publication No. CCDC 805877. Copies of thedata can be obtained, free of charge, on application to CCDC, 12Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033or e-mail: deposit@ccdc.cam.ac.uk.

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