Accepted Manuscript

Structural and physicochemical properties of 3-(3-carboxyphenylaminomethy lene)-2-methoxychroman-4-one Agnieszka Dziewulska-Kuaczkowska, Agata Bartyzel PII: DOI: Reference: To appear in: Received Date: Revised Date: Accepted Date: S0022-2860(12)00757-0 http://dx.doi.org/10.1016/j.molstruc.2012.08.013 MOLSTR 19146 Journal of Molecular Structure 17 April 2012 7 August 2012 7 August 2012

Please cite this article as: A. Dziewulska-Kuaczkowska, A. Bartyzel, Structural and physicochemical properties of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one, Journal of Molecular Structure (2012), doi: http:// dx.doi.org/10.1016/j.molstruc.2012.08.013

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STRUCTURAL AND PHYSICOCHEMICAL PROPERTIES OF 3-(3CARBOXYPHENYLAMINOMETHYLENE)-2-METHOXYCHROMAN-4-ONE Agnieszka Dziewulska-Kuaczkowska*, Agata Bartyzel Department of General and Coordination Chemistry, Faculty of Chemistry, Maria Curie-Skodowska University, M.C. Skodowskiej Sq. 2, 20-031 Lublin, Poland
*

e-mail: akulaczkowska@wp.pl

Abstract The 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one is a derivative of

chromanone. It was obtained in condensation reaction of 3-aminobenzoic acid with 3formylchromone. This ligand was characterized by elemental analysis, infrared and UV-VIS spectroscopy, thermal analysis and X-ray crystallography. The title compound is a new organic heterocyclic ligand which is thermal stable at the room temperature in air atmosphere. During heating on TG curves three steps of decomposition are observed. This process is connected with releasing following gases: CH3OH, CO2, CO and phenol. Compound crystallises in noncentrosymetric group. Molecules are connected by OHO bonds and form chains parallel to the c axis. Structure is stabilized by C-H and - interactions. Its solubility in water, methanol and DMF solutions in room temperature were also studied.

Keywords: chromanone, chroman-4-one, X-ray analysis, FTIR, UV-VIS, TG-DSC Introduction The chromanone is one of the important scaffold that can be obtained from natural compounds exhibiting favorable pharmacological properties such as antioxidant, antitumor, antibacterial, insecticidal and antifungal activities [1-3]. For example, according to Prakash et al. (2009) 2,3dimethoxy-3-hydroxy-2-(1-phenyl-3-(p-chlorophenyl)-4-pyrazolyl)chromanone, 2,3-dimethoxy3-hydroxy-2-(1-phenyl-3-(p-fluorophenyl)-4-pyrazolyl)chromanone and 2,3-dimethoxy-3hydroxy-2-(1-phenyl-3-(p-nitrophenyl)-4-pyrazolyl)chromanone have displayed antibacterial activity comparable to the commercial antibiotics (e.g. Linezolid, Cefaclor and Cefuroxime axetial) [4]. On the base of literature it is known that the derivatives of chromanone are HIV-1 1

1N inhibitors [5, 6] and also show potential anticancer activity [7]. Moreover, for example methyl-4-chromanone was found to exhibit strong activity in inhibiting in vitro cell growth of human K562 cells [8, 9]. Additionally, it was reported that some of chromanones are effective against lithium-epilocarpine induced status epilepticus, suggesting their potential application of the test compounds in the treatment of status epilepticus [10]. The broad-spectrum biological activities, interesting properties and potentially applications of derivative of chromanones are reason much attention around these compounds. One of way to synthesis of chromanones is reaction between 3-formylchromone and amine. The reaction of 4-oxo-4H-1-benzopyran-3carboxaldehyde and primary aromatic amines allows to obtain various types of products [11-24]. The type of these products depends on nature of used amine and/or experimental conditions. According to literature reaction between 3-formylchromone and primary aromatic amine leads to a mixture of the 3-(aryliminomethyl)chromone and 2-arylamino-3(arylaminomethylene)chroman-4-one what it causes that the isolation of pure compounds is difficult [11]. We synthesised pure derivatives of chromanones. This paper is a continuation of our recent studies of chromanones derivatives. Previous, the structures and characteristic of 3(anilinomethylene)-2-methoxychroman-4-one and 3-(1',4'-benzodioxan-6'-aminomethylene)-2methoxychroman-4-one were reported [25]. Recently we also presented details properties of 3(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one, which has chlorosubstituent in benzene ring. According to literature, the Clsubstituent shows negative inductive effect and has influence on electron density in aromatic ring [26, 27]. Now we obtained 3-(3carboxyphenylaminomethylene)-2-methoxychroman-4-one, which is new chromanone. In this paper, structure and physicochemical behaviours of title compound are presented. Additionally, the properties of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one with 3-(5carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one were also compared. The aim of comparison of these chromanones was check if chloro-substituent has influence on spectral and thermal properties of chromanone.

Experimental Methods and physical measurements Elemental analysis for C, H, N was performed using a Perkin-Elmer CHN 2400 analyser. The FTIR and UV-VIS spectra of compound were recorded over the range 4000-400 cm-1 and 200-

800 nm, respectively, using M80 spectrophotometer (Carl-Zeiss, Jena). The sample for the FTIR spectrum measurement was prepared as KBr disc. Thermal stability and decomposition of the analysed ligand was determined by Setaram Setsys 16/18 derivatograph, recording TG, DTG and DSC curves. The measurement was made at heating rate of 10 K min-1 with full scale. The sample (7.35 mg) was heated in ceramic crucible in air to 700 C. The TG-FTIR instrument consists of a TGA Q5000 analyzer (TA Instruments, New Castle, Delaware, USA) coupled with Fourier transform spectrometer Nicolet 6700 (Thermo Scientific) via a transfer line. The analysis was carried out at a heating rate of 20 C min-1 under nitrogen atmosphere at a flow rate of 50 mL min-1. In order to reduce the possibility of gases condensing along the transfer line, the temperature in the gas cell and transfer line were set to 250and 240 C, respectively. The sample (5.6780 mg) was heated up to 1000 C. The X-ray diffraction pattern was taken on a HZG4 (Carl Zeiss-Jena) diffractometer using Ni filtered CuK radiation. The measurement was made within the range 2 = 480 with a step equal to 0.5 . The X-rayan program was used for determining position and peak intensities. The TREOR program was used for calculating the unit cell parameters from the collection of data, which had been obtained from the X-rayan program [28]. Single-crystal diffraction data were collected on an Oxford Diffraction Xcalibur CCD diffractometer with graphite-monochromated MoK radiation ( = 0.71073). The temperature for the experiment was maintained at 100 K with an Oxford Cryosystem N2 gas-stream cooling device. The programs CrysAlis CCD and CrysAlis Red [29] were used for data collection, cell refinement and data reduction. A semiempirical absorptioncorrection based upon the intensities of equivalent reflections was applied, and the data were corrected for Lorentz and polarization effects. The structure was solved by direct methods using SHELXS97 and refined by the full-matrix least-squares on F2 using the SHELXL97 [30] (both operating under WinGX [31]). All non-hydrogen atoms were refined with anisotropic displacement parameters. H atoms bonded to O and N atoms were located in a difference Fourier map and refined isotropically. The positions of hydrogen atoms residing on carbon atoms were positioned geometrically and refined applying the riding model [CH = 0.950.98 and with Uiso(H) = 1.2 or 1.5 Ueq(C)]. In the least-squares refinements, the Flack parameter defined as |F| = (1 - x)|F(+)| + x|F(-)| was refined [32]. The absolute configuration was not determined because none heavier atoms than Si are present in structure and measurement was performed by using Mo radiation.

Crystal data and details of refinement are reported in Table 1, selected geometric parameters are given in Table 2. The molecular plots were drawn with SHELXTL [30] and Mercury [33]. The geometrical calculations were performed using PLATON program [34]. The solubility of ligand in various solvents at room temperature was determined spectrophotometrically using M80 spectrophotometer (Carl-Zeiss, Jena). Synthesis of chromanone The hot solution of 3-aminobenzoic acid (1.62 g, 5 mmol in 120 ml methanol) was added dropwise to a warm (40 C) solution 3-formylchromone (0.87 g, 5 mmol) in 60 ml methanol, and the solution was stirred at 50 C for 2 hrs. Next mixture has been left in 10 C for three days. The light yellow crystals were filtered off, washed several times with cold methanol and dried over CaCl2 for three days before measurements. Yield: above 64 %; m.p. 213 C. Materials The 3-aminobenzoic acid and 3-formylchromone used for the preparation of chromanone were obtained from Aldrich Chemical Company. The methanol and DMF was purchased from Polish Chemical Reagents in Gliwice (Poland). All solvent and chemical were reagent grade and were used without further purification.

Results and discussion The 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one was obtained as yellow crystals, which are stable up in room temperature in air atmosphere. Its structure (from monoand polycrystalline materials) and physicochemical properties were described.

Elemental purity Purity of compounds was established by elemental analysis and X-ray diffraction patterns. Elemental analysis (Anal. calc. for C18H15NO5 (M = 325.31 g mol-1) %: C, 66.39; H, 4.61; N, 4.30. Found: C, 66.27; H, 4.52; N, 4.30) shows that obtained 3-(3carboxyphenylaminomethylene)-2-methoxychroman-4-one is pure compound. The results from X-ray powder diffraction analysis confirmed that the analyzed sample represents a single phase. Moreover, during recrystallization significant changes in the crystal structure did not take place 4

(Fig. 1). The solution of powder diffraction is also orthorhombic, with the parameters

a = 6.055(5) , b = 15.914(5) , c = 16.058(6) and V = 1547.3 3 (F30 = 11.(0.024059,

114) [35]) giving evidence that the unit cell parameters are similar for single crystal and powder data.

Structural studies Title compound (Fig. 2) crystallises in noncentrosymmetric space group P212121 with one molecule in asymmetric unit (Table 1). The observed bond distances and angles are in the good agreement with the expected range of previously reported data (Table 2) [25,27,36,37]. As in closely related compounds, such as 3-(anilinomethylene)-2-methoxychroman-4-one, 3-(1,4benzodioxan-6-aminomethylene)-2-methoxychroman-4-one carboxyphenylaminomethylene)chroman-4-one, [27], [25], 2-methoxy-3-(4methoxy-3-[(3,4,5-

trimethoxyanilino)methylidene]-3,4-dihydro-2H-1-benzopyran-4-one [37] or 4-[(Z)-(2-ethoxy4-oxochroman-3-ylidene)methylamino]benzenesulfonamide monohydrate [38], the heterocyclic ring is puckered. A quantitative analysis of the ring conformation in 3-(3carboxyphenylaminomethylene)-2-methoxychroman-4-one was performed using the method of Cremer and Pople [39-41] for the calculation of parameters of puckering. A study of the torsion angles, asymmetric parameters and least squares plane calculations reveals that the pyranone ring is close to the skew-boat conformation 2S1 [39,41], where position 1 is signified as O in pyranone ring. This is confirmed by the puckering parameters [39,41], QT = 0.319(3) , 2= 210.02(6) and 2 = 115.8(5). In the structure, the nitrogen atom (N1) participates in intramolecular hydrogen bond (N1H1NO2), Table 3. As results of these interactions S(6) ring are generated. In previous reported compound (3-(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one [27]), the presence of this hydrogen bond together with another (N1-H1NCl) caused that HC11-N1H fragment lies in almost the same plane as pyran and phenyl (C12/C13/C14/C15/C16/C17) rings, corresponding dihedral angles were following 9.3(1) and 4.4(1). Also in structure of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one, pyran and phenyl rings are nearly coplanar with the HC10N1H moiety (6.5(1) and 1.5(1) , respectively). The presence of strong intermolecular hydrogen bonds between hydroxyl group and carbonyl oxygen atom (O5-H5OO2) and week (C17-H17O(4)) leads to the formation of infinite chains propagating along the c-axis direction (Fig. 3a). The zigzag adjacent chains are

linked via weak CHO (C8-H8O3methoxy) interactions which together with other weak interactions extend the above 1D infinite chains into a three-dimensional network. Additionally in the extended structure, weak C-H and - interactions further consolidate the structure, (see Fig. 3b). In the intermolecular C-H contacts, carbons share their attached hydrogen atoms with the aromatic system of a neighbouring phenyl rings. The first interaction is between C7-H7 and centroid Cg3(iv) of the ring defined by the atoms C12/C13/C14/C15/C16/C17 [symmetry code: (iv) 2-x, -1/2+y, 1/2-z]. In this interaction the C7Cg3(iv) distance is 3.617(3) and the bond angle equals 139. The second interaction involves C15-H15 and centroids Cg2(v) [symmetry code: (v) 1-x, 1/2+y, 1/2-z, Cg2 is the centroid of the C4/C5/C6/C7/C8/C9 ring] with the C15-Cg2(v) distance and the bond angle equal 3.557(3) and 131, respectively. The both C-H (phenyl) interactions can be classified as type II, according to the classification of Malone et al. [42]. The other weak - interaction is between C=O and (ring) (C3=O2Cg2(vi), symmetry code: (vi) -1+x, y, z,) with Oring centroid distance of 3.762 [43]. Comparing weak C-H and - interactions in both structures, 3-(3carboxyphenylaminomethylene)-2-methoxychroman-4-one and 3-(5-carboxy-2chlorophenylaminomethylene)-2-methoxychroman-4-one [27], it can be noticed that in the presented structure there are no the intermolecular - contacts between the two phenyl rings of neighbouring molecules which occur in chloro- derivative. The existence of these interactions in 3-(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one shows that the presence of chlorine atom highly increases the electron density of the benzene ring.

FT-IR analysis The IR spectral data of the studied chromanone are given in Table 4 and Fig. 4 and their assignments were made on the basis of the literature data [25, 27, 44-47]. The band at 1704 cm-1 with very strong intensity are assigned to (C=O) form -COOH group. In chloro- derivative this band is shifted to 1711 cm-1, what can be consequence of the presence of the electronegative atom (Cl) in the ring as well as non-existence in structure of week interaction C-HOcarbonyl. Moreover, in the structure of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one there are strong hydrogen bonds which influence on the stretching frequency of the bands characteristic of OH and NH bonds. The nitrogen atom participates in strong intramolecular hydrogen bond (NHOcarbonyl) which causes that band is shifted up to 2935 cm-1. In case of 3(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one the similar band is observed at 2961 cm-1. In this structure [27] the nitrogen atom is also involved in intramolecular 6

hydrogen bonds (NHOcarbonyl and NHCl) but the introduction of chlorine atom increase appearance of NH absorption. The similar influence can be notice in case of OH stretching vibration. The broad bands appear at 2988 cm-1 for title compound and 3004 cm-1 for chloroderivative which confirm existence of strong, intermolecular hydrogen bond. The presence of mentioned above hydrogen bonds (NHOcarbonyl and OHOcarbonyl) influence on absorption of carbonyl group in chromanone ring in both structure. The bands are shifted to lower wavelength and observed at 1640 cm-1 for 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one and 1644 cm-1 for 3-(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one. These results, from comparing infrared spectra of 3-(3-carboxyphenylaminomethylene)2-methoxychroman-4-one benzene ring. and 3-(5-carboxy-2-chlorophenylaminomethylene)-2methoxychroman-4-one, confirm influence of chloro- substituent on electron density of the

Thermal analysis The thermal stability of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one was studied at the range of 25-700 C in air atmosphere. The thermoanalytical curves TG/DTG and DSC its chromanone are presented on Fig. 5. The thermogram of ligand shows three decomposition steps. This compound is stable up to 128 C and after heating above this temperature the chromanone decomposes. The first stage of decomposition corresponds to the loss of methanol molecule. The observed mass loss for this step is 9.97 % and calculated is 9.86 %. The next step of decomposition is started above 278 C. This stage is connected with further decomposition and combustion of chromanone. During this process unstable, the intermediate product is formed. The experimental weight loss of this level is equal 20.56 %. The last step of thermal decomposition of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman4-one is started above 560 C. During this stage the broad exothermic peak is present on DSC curve and it is connected with combustion of the ligand residues. The total weight loss of thermal decomposition of analysed chromanone is 99.96 %. Results, from comparison thermal decomposition of 3-(3-carboxyphenylaminomethylene)-2methoxychroman-4-one and 3-(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman4-one, indicate that the chloro- substituent has not influence on thermal stability of chromanone in air atmosphere. As similar as for the described here chromanone, in their chloro- derivative decomposition process is started above 128 C with removing methoxy group from the pyranone

ring and stable compound is formed. The next change on the curves is observed at 264 C and it is connected with combustion of the ligand via intermediate formation [27].

TG-FTIR analysis The decomposition process of title chromanone with the gas product analysis was recorded in nitrogen atmosphere (Fig. 6). FTIR spectra of the gas phase products indicate that the decomposition of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one is connected with releasing of CH3OH, CO2, CO and phenol molecules as consequence of ligand defragmentation. The first bands appear on TG-FTIR spectra above 140 C and derive from methanol molecules. The characteristic vibration bands of methanol molecules are observed in the wavenumber around 3700, 2900 and 1100 cm-1. The TG-FTIR spectra, recorded above 320 C, show the absorption bands of CO2 molecules. The bands for CO2 molecules are observed at 2450-2250 cm-1. During the decomposition of analysed compound in higher temperature CO, methane and phenol are also generated. The double peak of band characteristic of CO molecule vibrations appears in the range of 2250-2000 cm-1. The bands characteristic of methane vibrations are observed at 3100-2750 cm-1. The band at 3663 cm-1 is due to the phenolic OH stretch and the band at 1184 cm-1 to the CO stretch. The wave band at 1576 cm-1 is due to the stretching vibrations of the aromatic ring (CArCAr). Furthermore, the peak at 743 cm-1 is characteristic for mono substituted benzene [48-53]. All bands characteristic of phenol are very weak because of small amount of sample used for analysis.

UV-VIS spectroscopy and solubility The electronic spectra of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one in various solutions (methanol, water and DMF) were recorded in the range of 200-600 nm. The concentration of solutions was 1 10-5 mol dm-3 (Fig. 7). The spectrum of analysed chromanone in methanol solution shows one broad peak with maximum at 420 nm. This band is probably due to n- * transition of the =CH-NH- group. In the spectrum, registered in water solution, two bands appear the first at 300 and the second (small and broad) at 380 nm. Two bands were also observed for the spectrum of 3-(3carboxyphenylaminomethylene)-2-methoxychroman-4-one in DMF solution (260 and 380 nm). The bands at lower frequencies for water and DMF solutions may due to - * transition of the benzene ring from aromatic amine or due to - * transitions within chromanone ring. The bands

at 380 in these solutions are assigned as n- * transition of the =CH-NH- group. As shown at the registered spectra (Fig. 7) compound exhibits solvatochromism [54,55]. The result from comparison of UV-VIS spectra of 3-(3-carboxyphenylaminomethylene)2-methoxychroman-4-one with 3-(5-carboxy-2-chlorophenylaminomethylene)-2methoxychroman-4-one in methanol solution indicates that chloro- substituent as auxochrome changes both the wavelength and intensity of maximum absorption. On UV-VIS spectrum of 3(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one in methanol solution two peaks, at 258 nm and 382 nm, are observed. It can be noticed that a hypsochromic effect is observed for the chloro-chromanone derivative relative to chromanone. The maximum of peak which was assigned to n- * transition of the =CH-NH- group is shifted from 420 nm to 382 nm. The molar absorptivity () values are equal 17524 and 30018 L mol-1 cm-1 for chromanone (max = 420 nm) and chloro-chromanone derivative (max = 382 nm), respectively. The solubilities of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one in water, methanol and DMF at 293K were determined spectrophotometrically by measuring the concentration of chromanone in saturated solutions. The calibration equations were following: A=18312C-0.0094 (R2 = 0.9966) for methanol, A=9082.5C+0.0333 (R2 = 0.9966) for water and A=28388C-0.0238 (R2 = 0.9999) for DMF, where A is absorbance and C is the chromanone concentration in mol L-1. The values of solubility of studied chromanone are changed: 4.74 10-4 (water) < 2.17 10-3 (methanol) < 6.09 10-1 (DMF) mol L-1. The solubility of 3-(5-carboxy-2chlorophenylaminomethylene)-2-methoxychroman-4-one was measured in similar method and solvent. The values of solubility of chromanone with chloro- substituent are following: 7.06 10-4 (water) < 1.48 10-3 (methanol) < 1.76 10-1 (DMF) mol L-1. The comparison obtained results indicates that the solubilities 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one and 3-(5-carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one are similar. The entering Cl-substituent in the benzene ring has not significant influence on solubility of title chromanone.

Conclusion The structure and properties of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one are presented. Compound crystallises in noncentrosymetric group. Molecules are connected by OHO bonds and form zigzag, infinite chains parallel to the c axis. The solubility of title compound increases with decreasing solvent polarity. Additionally spectral and thermal 9

behaviours

of

3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one were

and

3-(5The

carboxy-2-chlorophenylaminomethylene)-2-methoxychroman-4-one

compared.

obtained results show that presence of chlorine atom increases the electron density of the benzene ring and influences on weak interactions on the crystal structure. These interactions as well as the present of chloro- substituent in benzene ring can be also reflected on the UV-VIS and IR spectra. The bands characteristic for groups contain atoms involved in hydrogen bonds and week C-H and - interactions are shifted to higher frequencies. In case of UV-VIS analysis it can be noticed that the chloro- substitution cause hypsochromic effect. On the other hand the chloro- substituent does not affect solubility and thermal stability in air of studied chromanone.

Supplementary material Crystallographic data have been deposited with the CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44 1223 366033; e-mail: deposit@ccdc.cam.ac.uk or www://www.ccdc.cam.ac.uk) and are available on request, quoting the deposition number CCDC 874357.

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Captions for illustrations Fig. 1 Dependence intensity versus 2 for calculated and experimental data of 3-(3carboxyphenylaminomethylene)-2-methoxychroman-4-one. Fig. 2 Perspective view of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one with the atom numbering scheme. Displacement ellipsoids are draw at the 50% probability level. Dashed lines indicate intramolecular hydrogen bonds. Fig. 3 (a) Part of the crystal structure of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4one showing intermolecular hydrogen bonds and formation of 1D chains along the c-axis. (b) Part of the crystal structure of title compound showing CH(ring) and C=O(lone pair)(ring) stacking interactions as dashed lines. Symmetry codes: (iv) 2-x, -1/2+y, 1/2-z; (v) 1-x, +y, 1/2-z; (vi) -1+x, y, z. Fig. 4 FTIR spectrum of analysed compound. Fig. 5 TG, DTG and DSC curves for studied ligand in air. Fig. 6 The FTIR spectra of gaseous products evolved during the decomposition of analysed chromanone Fig. 7 UV-VIS spectra of 3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one

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Table 1 Crystal data and structure refinement for 3-(3-carboxyphenylaminomethylene)-2methoxychroman-4-one. Empirical formula Formula weight Temperature K Crystal system Space group a () b () c () Volume (3) Z Calculated density (g cm-3) (mm-1) Absorption correction F(000) Crystal size (mm) range () Index ranges Reflections collected/unique Rint Absolute structure parameter Data/restraints/parameters GooF on F2 Final R indices[I>2(I)] R indices(all data) max; min (e -3) C18H14NO5 325.31 100(2)K orthorhombic P212121 6.005(1) 15.757(1) 15.819(1) 1496.7(2) 4 1.444 0.106 multi-scan 680 0.30x0.15x0.05 2.58 to 27.47 -7<=h<=7 -20<=k<=19 -12<=l<=20 6081/3301 0.0443 -0.1(15) 3301/0/225 0.876 R1 = 0.0435, wR2 = 0.0884 R1=0.0734, wR2=0.1128 0.396; -0.393

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Table 2 Selected bond lengths [A] and angles []. Bond lengths () C(1)-O(1) C(1)-O(3) C(1)-C(2) C(2)-C(3) C(2)-C(11) C(3)-O(2) C(3)-C(4) C(10)-O(3) C(11) -N(1) C(12)-N(1) Bond angles () O(1)-C(1)-C(2) C(1)-C(2)-C(3) C(2)-C(3)-C(4) O(4)-C(18)-O(5) Torsion angles () O(1)-C(1)-C(2)-C(3) C(1)-C(2)-C(3)-C(4) C(2)-C(3)-C(4)-C(9) -26.6(4) 2.4(4) 10.1(4) C(3)-C(4)-C(9)-O(1) C(4)-C(9)-O(1)-C(1) C(9)-O(1)-C(1)-C(2) 3.4(4) -29.9(4) 40.0(3) 112.8(2) 120.1(3) 117.4(2) 123.8(3) C(3)-C(4)-C(9) C(1)-O(1)-C(9) O(1)-C(9)-C(4) 119.2(3) 117.3(2) 121.6(3) 1.442(3) 1.394(3) 1.506(4) 1.417(4) 1.378(4) 1.266(3) 1.463(4) 1.441(4) 1.339(4) 1.409(3) C(4)-C(5) C(4)-C(9) C(5)-C(6) C(6)-C(7) C(7)-C(8) C(8)-C(9) C(9)-O(1) C(18)-O(4) C(18)-O(5) 1.400(4) 1.400(4) 1.383(4) 1.381(4) 1.386(4) 1.392(4) 1.378(3) 1.212(3) 1.331(4)

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Table 3 Hydrogen-bond geometry [, ]. D-HA N(1)-H(1N)O(2) O(5)-H(5O)O(2)(i) C(8)-H(8)O(3)(ii) C(17)-H(17)O(4) (iii) d(D-H) 0.96(3) 0.90(4) 0.95 0.95 d(HA) 1.85(3) 1.69(4) 2.60 2.45 d(DA) 2.612(3) 2.579(3) 3.434(4) 3.366(4) DHA 134(3) 167(3) 147 162

Symmetry codes: (i) -x+1/2,-y+1,z-1/2; (ii) x+1, y, z; (iii) x+1/2, -y+1, z+1/2

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Table 4 The frequencies of the maxima of the absorption bands for studied ligand (1) and 3-(5-carboxy2-chlorophenylaminomethylene)-2-methoxychroman-4-one (2). Frequency [cm-1] 1 2 3064 vw 3083 vw 3020 vw 3070 vw 2988 vw 3004 vw 2935 w 2961 w 2900 w 2922 w 2824 w 2823 w 2580 w 1704 vs 1711 vs 1640 vs 1604 vs 1592 vs 1548 m 1496 m 1468 vs 1444 s 1401 m 1388 m 1364 w 1344 m 1296 vs 1280 s 1248 s 1228 s 1188 m 1156 m 1644 vs 1604 vs 1588 vs 1552 m 1500 m 1468 vs 1448 s 1416 s 1388 m 1368 m 1340 m 1300 vs 1284 s 1236 w 1216 s 1180 vs 1156 m Assignment (C-H) (C-H) (OH) [OH...O] (NH) [NH...O] as(CH3) s(CH3) (O...H) (C=O) from -COOH (C=O)chromanone carbonyl (C=C) (C=C), w(N-H) (C=C) (C=C) (C=C), as(CH3) (C-O), s(C-H) (C-OH) (C-N) (C-CHO), s(CH3) (C-C), (CH) (C-C), as(C-O-C), (C-N), (CH) as(C-O-C), (C-C) (C-C) as(CH), (C-N) (COC) (CH), (COC) Frequency [cm-1] 1 2 1148 m 1112 s 1104 m 1068 s 1068 s 1044 m 1020 s 1020 s 976 m 980 m 968 m 968 w 940 s 940 s 872 m 860 m 824 m 812 m 788 w 764 m 752 vs 708 m 700 m 676 m 548 m 540 m 500 m 440 w 416 w 872 m 860 m 832 w 812 m 784 w 764 m 752 vs 703 m 700 m 683 m 619 m 561 w 537 w 460 m 436 w 410 w Assignment (O-(CH3)) (OCC) s(C-O-C), wach(CH) (C-Cl) (C-C) (C-C), (C-CHO) (C-C) (CCC), (CH) (CH) (CCC), (CH) (CH) (CH) (CH) (CH) (CH), w(N-H) (CH) (CH) (CH) (C-Cl) (COC), (HC=O) (COC), (HC=O) (COC) (C=O) (C=O)

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Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Highlights The new organic ligand has been synthesized and its physicochemical properties are described. This ligand (3-(3-carboxyphenylaminomethylene)-2-methoxychroman-4-one) is the derivative of parent chromanone compounds. > Molecules, contain in their structure chromanone ring, have attracted attention because they show interesting biological and pharmacological properties.

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