ft-ir, ft-raman and dft calculations of...

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Research ArticleReceived: 3 July 2008 Accepted: 2 October 2008 Published online in Wiley Interscience: 19 December 2008

(www.interscience.wiley.com) DOI 10.1002/jrs.2159

FT-IR, FT-Raman and DFT calculations of3-{[(4-fluorophenyl)methylene]amino}-2-phenylquinazolin-4(3H)-oneC. Yohannan Panicker,a∗ K. R. Ambujakshan,b Hema Tresa Varghese,c

Samuel Mathew,d Subarna Ganguli,e Ashis Kumar Nandaf andChristian Van Alsenoyg

Fourier transform (FT)-Raman and Fourier transform infrared (FT-IR) spectra of 3-{[(4-fluorophenyl)methylene]amino}-2-phenylquinazolin-4(3H)-one were recorded and analyzed. The vibrational wavenumbers of the title compound were computedusing the B3LYP/6-31G∗ basis and compared with the experimental data. The prepared compound was identified by NMR andmass spectra. The simultaneous IR and Raman activation of the C=O stretching mode shows a charge transfer interactionthrough a π -conjugated path. The first hyperpolarizability and infrared intensities are reported. The assignments of the normalmodes are done by potential energy distribution (PED) calculations. Copyright c© 2008 John Wiley & Sons, Ltd.

Supporting information may be found in the online version of this article.

Keywords: quinazoline; IR spectra; Raman spectra; DFT calculations; PED

Introduction

Compounds containing a fused quinazoline or isoquinoline ringbelong to a broad class of compounds that has received aconsiderable attention over the past years due to their widerange of biological activities.[1,2] Some of the aminoquinazo-line derivatives were found to be inhibitors of the tyrosinekinase,[3,4] or dihydrofolate reductase enzymes,[5,6] and so theywork as potent anticancer agents. They are also used to de-sign medicines against hypertension and malaria and to fightinfections involving AIDS.[7] Quinazolines have been frequentlyused in medicine because of their wide spectrum of biologicalactivities.[8] Several quinazoline derivatives have been reportedfor their antibacterial, antifungal, anti-HIV,[9,10] anthelmintic,[11]

central nervous system (CNS) depressant,[12] antitubercular,[13]

hypotensive,[14] anticonvulsant,[15] anti-fibrillatory,[16] diuretic,[17]

and antiviral[18 – 20] activities. Antitumor activities are also re-ported for 2,3-dihydro-2-aryl-4-quinazolines.[21,22] Some reportshave suggested that 2-styrylquinazolin-4-ones[23,24] could be ef-fective inhibitors of tubulin polymerization. The 2,3-disubstitutedquinazolones have been predicted to possess antiviral and an-tihypertensive activities.[25] Synthesis of vascinone, a naturallyoccurring bioactive alkaloid having a quinazolone system, hasbeen reported very recently.[26] Among a wide variety of nitrogenheterocycles that have been explored for developing pharma-ceutically important molecules, the quinazolines have played animportant role in medicinal chemistry and subsequently emergedas a pharmacophore.[27] Bacterial infections often produce in-flammation and pain. In normal practice, two groups of agents(chemotherapeutic, analgesic and anti-inflammatory) are pre-scribed simultaneously. Compounds possessing all three activitiesare not common. Quinazolines and quinazoline derivatives exhibitpotent antimicrobial[28] and central nervous systems activities

such as anti-inflammatory[29] and anticonvulsant.[30] Quinazolinesare widely used for the extraction and analytical determinationof metal ions. Nitraquazone, a quinazoline derivative, has beenfound to possess potent phosphodiesterase inhibitory activity,[31]

which is potentially useful in the treatment of asthma.[32] Ala-garsamy et al.[33] have reported the synthesis and analgesic,anti-inflammatory and antibacterial activities of some novel 2-phenyl-3-substituted quinazolin-4(3H)ones. Nanda et al.[34] havereported the antibacterial activity and quantitative structureactivity relationship (QSAR) studies of some 3-(arylideneamino)-2-phenyl quinozoline-4(3H)-ones. Ab initio quantum mechanicalmethod is at present widely used for simulating the IR spectrum.

∗ Correspondence to: C. Yohannan Panicker, Department of Physics, TKM Collegeof Arts and Science, Kollam, Kerala 691005, India.E-mail: [email protected]

a Department of Physics, TKM College of Arts and Science, Kollam, Kerala 691005,India

b Department of Physics, MES Ponnani College, Ponnani South, Malappuram,Kerala, India

c Department of Physics, Fatima Mata National College, Kollam, Kerala 691001,India

d Department of Physics, Mar Thoma College, Thiruvalla, Kerala, 689103, India

e BCDA College of Pharmacy, 78, Jessore Road, Hridaypur, Barasat, Kolkata, WestBengal 700127, India

f Department of Chemistry, North Bengal University, Raja Rammohunpur,Siliguri, 734013, West Bengal, India

g University of Antwerp, Chemistry Department, Universiteitsplein 1, B2610Antwerp, Belgium

J. Raman Spectrosc. 2009, 40, 527–536 Copyright c© 2008 John Wiley & Sons, Ltd.

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C. Y. Panicker et al.

Such simulations are such indispensable tools to perform nor-mal coordinate analysis that modern vibrational spectroscopy isunimaginable without involving them. Besides, very few spectro-scopic studies have been reported so far on the heteroaromaticbicyclics. To obtain reliable wavenumber assignments, a detailedvibration analysis is required. Considering the above facts, in thepresent study the FT-IR, FT-Raman and theoretical calculations ofthe wavenumber values of the title compound are reported.

Experimental

Synthesis of the title compound involved three steps: benzoy-lation with simultaneous cyclization, addition of hydrazine andfinally condensation to form a Schiff base. Thus, anthranilic acidwas treated with benzoyl chloride in the presence of pyridineto undergo cyclization forming 2-phenyl-4H-benzo[d][1,3]oxazin-4-one, which on condensation with hydrazine hydrate yielded3-amino-2-phenylquinazolin-4(3H)-one. The latter compoundwas then treated with suitable substituted benzaldehydes in thepresence of ethanol to form the title compound. Synthesis of thetitle compound, 3-{[(4-fluorophenyl)methylene]amino}-2-phenylquinazolin-4(3H)-one has been reported elsewhere[34] in subse-quent experiments it was observed that solvent-free synthesisyielded stoichiometric conversion to the product. In this procedureequimolar amounts of 3-amino-2-phenylquinazolin-4(3H)-oneand 4-flurobenzaldehyde were triturated in a pestle with a mortarand the mixture was transferred into a vial; the vial was heated inan oil bath for 30 min at about 80 ◦C. The product thus formed wasalmost pure for subsequent use. However, it was crystallized froman ethanol/benzene: 5 : 1 mixture to obtain the crystalline product.

Purity of the compound was checked by thin-layer chromatog-raphy (TLC), using benzene and ethyl acetate as mobile phase inthe ratio 7 : 3. Iodine vapor was used as the detecting agent. Themelting point was determined in open capillary tubes on a ThomasHoover apparatus and was uncorrected: m.p.166 ◦C. Mass spectrawere recorded on a FAB, JEOL SX 102 mass spectrometer, and NMRspectra were recorded on a Bruker-Avance 300 MHz FT-NMR spec-trometer with CDCl3 as solvent and TMS as internal standard, andthe peak assignments were done on the basis of TOCSY, COSY andHSQC(HETCORR) spectra in addition to 13C spectra. The FT-IR spec-trum (Fig. 1) was recorded on a DR/Jasco FT/IR-6300 spectrometerwith KBr pellets. The FT-Raman spectrum (Fig. 2) was obtainedon a Bruker RFS 100/S instrument (Germany). For excitation ofthe spectrum the emission fron a Nd : YAG laser was used, withexcitation wavelength 1064 nm, maximum power 150 mW andresolution 4 cm−1. Measurements were made on solid samples.

FAB MS (m/z) 344 [M + 1]; 1H NMR: 7.1 (H-38,39), 7.41 (H-17,18),7.45 (H-19), 7.49 (H-9), 7.53 (H-21), 7.54 (H-34,36), 7.7 (H-14,20), 7.8(H-8), 8.3 (H-7), 9.04 (s, 1H, H–C=N), 7.8 Hz (J7,9), 0.9 Hz (J7,8), 0 Hz(J7,21), 6.3 Hz (J9,8), 1.8 Hz (J9,21), 8.7 Hz (J36,39 34,38); 13C NMR: 166.30 (=C(F)–, C-37), 164.84 (H–C=N), 153.97 (C-23), 153.90(C-25), 146.60 (C-3), 134.55 (C-10), 134.15 (C-5), 131.00 (C-31,32),130.89 (C-16), 130.50 (C-30), 129.30 (C-11,12), 128.98 (C-13,15),127.68 (C-6), 127.20 (C-1), 126.79 (C-4), 121.50 (C-2), 116.33 (C-33,35); Anal./calculated: C, 73.46%; H, 4.11%; N, 12.24%. Found: C,73.50%; H, 4.10%; N, 12.18%. Molecular formula C21H14N3OF.

Computational Details

The vibrational wavenumbers were calculated using the Gaus-sian03 software package on a personal computer.[35] The density

functional theoretical (DFT) computations were performed at theB3LYP/6-31G∗ level of theory to get the optimized geometry(Fig. 3) and vibrational wavenumbers of the normal modes of thetitle compound. Calculations were carried out with Becke’s three-parameter hybrid model using the Lee–Yang–Parr correlationfunctional (B3LYP) method. Molecular geometries were fully opti-mized by Berny’s optimization algorithm using redundant internalcoordinates. Harmonic vibrational wavenumbers were calculatedusing analytic second derivatives to confirm the convergence tominima on the potential surface. At the optimized structure of theexamined species, no imaginary wavenumber modes were ob-tained, proving that a true minimum on the potential surface wasfound. The DFT hybrid B3LYP functional tends also to overestimatethe fundamental modes; therefore scaling factors have to be usedfor obtaining a considerably better agreement with experimentaldata. Therefore, a scaling factor of 0.9613 was uniformly appliedto the B3LYP-calculated wavenumbers. The observed disagree-ment between theory and experiment could be a consequence ofthe anharmonicity and of the general tendency of the quantumchemical methods to overestimate the force constants at the exactequilibrium geometry. The potential energy distribution (PED) iscalculated with the help of GAR2PED software package.[36] Param-eters corresponding to optimized geometry of the title compound(Fig. 3) are given in Table S1 (Supporting Information).

Results and Discussion

IR and Raman spectra

The observed IR and Raman bands with their relative intensities,scaled wavenumbers and assignments are given in Table 1. Thecarbonyl stretching wavenumber has been the most extensivelystudied by infrared spectroscopy. The most characteristic bandof esters arising from the C=O stretching vibration occurs at1750 ± 50 cm−1 with strong to very strong intensity.[37] Forthe title compound, the υC=O mode is seen as a strongband at 1673 cm−1 in the IR spectrum and at 1661 cm−1 inthe Raman spectrum. But the electron-releasing effect in theC=O double bond causes polarizability change during vibration,making the Raman band intensity comparable to that of the IRband. Here, the intramolecular charge transfer takes place viaa conjugated phenyl ring path,[38] which makes phenyl ring-stretching mode at 1604 cm−1 simultaneously active in IR andRaman spectra. The deformation bands of the C=O are alsoidentified (Table 1).

The C=N stretching skeletal bands[39 – 41] are observed inthe range 1627–1566 cm−1. For the title compound the bandobserved at 1546 cm−1 in the IR spectrum is assigned to the υC=Nmode. For conjugated azines[42] the υC=N mode is reportedat 1553 cm−1. DFT calculations give these modes at 1561 and1535 cm−1.

Fluorine atoms directly attached to an aromatic ring giverise to bands[43] in the region 1270–1100 cm−1. Many of thesecompounds, including the simpler ones with one fluorine onlyon the ring,[43] absorb near 1230 cm−1. The υC–F is reported at1233 (IR) and 1244 cm−1 (HF)[44] and at 1227 (IR) and 1239 (HF)[45]

for fluorophenyl compounds. In the present case, experimentallyno band is observed, whereas the DFT calculations give this υC–Fmode at 1217 cm−1.

Primary aromatic amines with nitrogen directly on the ringabsorb at 1330–1260 cm−1 because of the stretching of thephenyl C–N bond.[43] For the title compound, the υC3 –N22

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Vibrational spectra of 3-{[(4-fluorophenyl)methylene]amino}-2-phenylquinazolin-4(3H)-one

Figure 1. FT-IR spectrum of 3-{[(4-fluoro phenyl)methylene]amino}-2-phenylquinazolin-(3H)-one.

Figure 2. FT-Raman spectrum of 3-{[(4-fluoro phenyl)methylene]amino}-2-phenylquinazolin-(3H)-one.

mode is observed at 1246 cm−1 in IR, at 1250 cm−1 in Ramanspectrum and at 1248 cm−1 theoretically. This mode is not purebut contains significant contributions from other modes. The C–Nstretching bands[46] are reported in the range 1100–1300 cm−1.In the present case, the υC25 –N26, and υC23 –N26 stretchingbands are observed at 1273, 1109 cm−1 in the IR spectrum andat 1257, 1110 cm−1 theoretically. υN–N has been reported at1115 cm−1 by Crane et al.,[47] at 1121 cm−1 by Bezerra et al.[48] and

at 1130 cm−1 by El-Behery and El-Twigry.[49] The band observed at∼1093 cm−1 in both spectra is assigned to the υ N26 –N27 mode.

Since the identification of all the normal modes of vibration oflarge molecules is not trivial, we tried to simplify the problem byconsidering each molecule as a substituted benzene. Such an ideahas already been successfully utilized by several workers for thevibrational assignments of molecules containing multiple homo-and heteroaromatic rings.[44,50 – 55] In the following discussion, the

J. Raman Spectrosc. 2009, 40, 527–536 Copyright c© 2008 John Wiley & Sons, Ltd. www.interscience.wiley.com/journal/jrs

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Figure 3. Optimized geometry of 3-{[(4-fluoro phenyl)methylene]amino}-2-phenylquinazolin-(3H)-one. This figure is available in colour online atwww.interscience.wiley.com/journal/jrs.

mono-, ortho- and para-substituted phenyl rings are designatedas PhI, PhII and PhIII, respectively. The modes in the three phenylrings will differ in wavenumber, and the magnitude of splittingwill depend on the strength of interactions between differentparts (internal coordinates) of the three rings. For some modes,this splitting is so small that they may be considered as quasi-degenerate, and for other modes a significant amount of splitting isobserved. Such observations have already been reported.[51 – 53,56]

The existence of one or more aromatic ring in a structureis normally determined from the C–H and C=C–C ring relatedvibrations. The C–H stretching occurs above 3000 cm−1 and istypically exhibited as multiplicity of weak to moderate bands,compared with the aliphatic C–H stretching.[57] In the presentcase, the DFT calculations give υC–H modes of the phenyl ringsin the range 3072–3124 cm−1. The bands observed at 3000, 3055,3091, 3164, 3200 cm−1 in the IR spectrum and at 3034, 3077 cm−1

in the Raman spectrum are assigned to the υC–H modes of thephenyl rings.

Corresponding to the υC28 –H29 mode, no bands are experi-mentally observed, and the DFT calculations give this mode at3111 cm−1 with a PED contribution of 95%.

The benzene ring possesses six ring-stretching vibrations, ofwhich the four with the highest wavenumbers (occurring near1600, 1580, 1490 and 1440 cm−1) are good group vibrations.With heavy substituents, the bands tend to shift to somewhatlower wavenumbers. In the absence of ring conjugation, theband at 1580 cm−1 is usually weaker than that at 1600 cm−1.In the case of C=O substitution, the band near 1490 cm−1 canbe very weak. The fifth ring-stretching vibration is active near1315 ± 65 cm−1, a region that overlaps strongly with that ofthe CH in-plane deformation. The sixth ring-stretching vibration,or the ring-breathing mode, appears as a weak band near1000 cm−1 in mono-, 1,3-di- and 1,3,5-trisubstituted benzenes.In the otherwise substituted benzenes, however, this vibration

is substituent sensitive and difficult to distinguish from the ringin-plane deformation.[37]

The υPh modes are expected in the regions 1285–1610,1260–1615 and 1280–1630 cm−1 for PhI, PhII and PhIII rings,respectively.[37] The υPh modes are observed at 1591, 1451, 1318,1055 cm−1 in the IR spectrum, 1450, 1318, 1050 cm−1 in the Ramanspectrum, 1595, 1574, 1445, 1316, 1083, 1027 cm−1 theoreticallyfor ring Ph I; at 1604, 1266, 1018 cm−1 in IR spectrum, 1604,1552, 1250, 1034 cm−1 in Raman spectrum and 1600, 1555, 1465,1341, 1248, 1019 cm−1 theoretically for ring PhII; and at 1645,1511, 1409 cm−1 in the IR spectrum, 1636, 1586, 1511, 1416 cm−1

in the Raman spectrum and 1603, 1583, 1506, 1405, 1323 cm−1

theoretically for ring PhIII.The ring-breathing mode of the para-disubstituted benzenes

with entirely different substituents[58] has been reported in theinterval 780–880 cm−1. For the title compound, this is confirmedby the band in the infrared spectrum at 873 cm−1 and at 861 cm−1

theoretically, which finds support from the computational results.The ring-breathing mode of monosubstitued benzene[37] PhIappears near 1000 cm−1, and the band observed at 1050 cm−1

in the Raman spectrum, 1055 cm−1 in the IR spectrum andat 1027 cm−1 theoretically is assigned to this mode. In orthodisubstitution, the ring-breathing mode has three wavenumberintervals according to whether both substituents are heavy, orone of them is heavy while the other is light, or both of themare light. In the first case, the interval is 1100–1130 cm−1, inthe second case it is 1020–1070 cm−1, while in the third case[58]

it is 630–780 cm−1. In the present case, the band observed at1018 cm−1 in IR, 1034 cm−1 in Raman and 1019 cm−1 by DFT isassigned as the ring-breathing mode of PhII.

The CH out-of-plane deformations of the phenyl rings[37] areobserved between 1000 and 700 cm−1. Generally, the CH out-of-plane deformations with the highest wavenumbers have weakerintensity than those absorbing at lower wavenumbers. The γ CH


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Table 1. Calculated vibrational wavenumbers (scaled), measured infrared and Raman band positions and assignments for 3-{[(4-fluorophenyl)methylene]amino}-2-phenylquinazolin-4(3H)-one

υ (DFT) (cm−1) υ (IR) (cm−1) υ (Raman) (cm−1) IR Intensity Assignments of normal modes with PED(%)a

3124 3200 m 9.75 υCH I (69), υCH III(21)

3124 3164 m 3.47 υCH III(70), υCH I (20)

3121 4.82 υCH III(87)

3117 9.89 υCH I(87)

3116 19.82 υCH II (91)

3132 5.60 υCH II(93)

3111 2.38 υC28H29(95)

3109 0.77 υCH III(95)

3097 3091 m 36.15 υCH I (95)

3095 20.67 υCH II(90)

3084 5.37 υCH III(93)

3083 15.40 υCH I (93)

3080 3055 m 3077 w 5.20 υCH II (93)

3072 3000 w 3034 vw 0.01 υCH I(98)

2873 mbr

2822 m Combination bands

2746 w

2670 w

2600 sbr

2492 w

2415 w

2364 w

2314 w

2237 w

2161 w

2110 w

1983 w

1953 sbr

1901 sbr

1805 w

1729 w

1616 1673 s 1661 m 132.08 υC23O24(37)

1603 1645 s 1636 w 8.26 υPh III (23)

1600 1604 s 1604 vvs 181.81 υPh II (12), υPh III (23)

1595 1591 m 5.71 υPh I (38)

1583 1586 vvs 0.38 υPh III (45)

1574 34.33 υPh I (59), δCHC I (20)

1561 100.67 υN27C28(44)

1555 1552 s 9.42 υPh II(48)

1535 1546 m 341.92 υ N22C25(44)

1506 1511 s 1511 m 51.59 δCHC III(52), υPh III (10)

1494 22.91 δCHC I (60)

1465 59.99 δCHC II (41), υPh II (15)

1462 4.78 δCHC II(43)

1445 1451 s 1450 m 9.91 δCHC I (55), υPh I (25)

1405 1409 m 1416 m 4.79 υPh III (42), δCHC III (38)

1367 1373 m 1364 w 9.54 δN27H29C28(43), δC30H29C28(43)

1341 50.98 υPh II (42)

1336 38.64 δCHC I (36)

1323 51.25 υPh III (52)

1316 1318 m 1318 m 5.64 υPh I (23)

1308 1295 m 25.76 δCHC III(42)

1303 1280 s 15.70 δCHC III(22)

1257 1273 m 122.95 υC25N26(24)

(continued overleaf )


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Table 1. (Continued)


1248 1246 m 1250 w 8.29 υC3N22(19), υPh I (16), υC2C23(11),δCHC II(20)

1231 1238 m 1233 s 123.16 υC28C30(26)

1217 45.51 υC37F40(25)

1213 10.42 υC37F40(14), δCCC III(78)

1194 1191 m 10.66 δCHC I(78)

1177 0.30 δCHC I(80)

1169 1164 m 1170 w 4.31 δCHC II(67)

1161 1154 m 1160 m 59.49 δCHC III(71)

1117 1126 m 40.78 υN26N27(12), δCHC II(22),υC23N26(10),

1110 1109 m 6.78 υC25N26(20), υC23N26(18),δC23C27C26(13), δC25N27N26(13)

1104 5.14 δCHC III(42), υPh III(11)

1093 1092 m 1093 m 23.15 υN26N27(13), δCCC II(60),υC23N26(11)

1083 20.84 υPh I (26), δCHC I (10)

1027 1055 m 1050 w 6.28 υPh I(47), δCCC I(36)

1019 1018 w 1034 w 11.82 υPh II(58), δCHC II(11)

1009 5.37 δCCC III(48), υPh III (11)

1003 1002 m 21.09 γ H29N27C30C28(56), τN26N27C28H29 (18),τN26N27C28C30(18)

999 1000 w 0.01 γ HCCC II (86), τCCCC II (13)

997 1.27 δCCC I (52)

992 991 w 0.20 γ HCCC I (67), τCCCC I (16)

975 982 w 1.25 γ HCCC III (80)

972 973 w 1.95 γ HCCC II (85)

966 966 w 2.00 γ HCCC I (90)

949 2.89 γ HCCC III (12), υC23N26(12),δC23C25N26(10), δN26C22C25(10),δC25C3N22(10), δN22C2C3(10),δC3C23C2(10), δC2N26C23(10)

948 1.65 γ HCCC III (60), τCCCC III (22)

927 922 m 924 m 4.70 γ HCCC I (74), τCCCC I (11)

898 900 w 39.06 δCCC II (60), υN26N27(13),δN26C28N27(11)

888 891 w 886 w 1.22 γ HCCC II (71)

861 873 w 4.30 υPh III (15), δCCC II (26)

843 852 w 4.74 γ HCCC I (83)

837 36.22 υPh II (16)

837 841 m 39.55 γ HCCC III(58)

823 818 w 8.75 γ HCCC III(89)

788 800 w 792 m 2.45 τQRing(29), τCCCC II(18),γ OH24C2N26C23(16)

779 17.20 γ HCCC II (30), τCCCC I (30)

777 767 m 9.22 υC37F40(16), δCCC III(36)

773 755 w 748 w 62.73 τCCCC I (17), τCCCC II (15), γ HCCCII(11), γ HCCC I(11)

712 716 w 10.75 τCCCC III(50), γ C28CCC III (10),γ F40CCC III (10)

706 7.30 τCCCC III (66)

699 702 m 700 w 38.82 τCCCC III (34), γ C10N22N26C25(15),τCCCC II(12)

693 682 w 686 w 19.76 τCCCC I (52)

676 6.36 γ O24C2N26C23(26), τCCCC II (22)

672 671 w 8.43 δCCC I (24), δCCC II (13),γ O24C2N26C23 (10)

655 646 w 14.89 δCCC II (20), δC2O24C23(13),δN26O24C23(13), δC23N27N26(11),δC25N27N26(11), δNC10C25(10), τCCCC I (10)


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Table 1. (Continued)


636 636 w 0.65 δCCC III (73)

626 609 w 606 w 0.07 δCCC I (82)

582 584 w 580 w 1.02 δCCC II (45), δCCC I (14)

568 582 s 15.63 δQRing(20), δCCC III (16),

544 546 m 536 w 8.32 τCCCC II(47)

525 6.31 τCCCC III (56), γ F40C33C35C37(28),γ C28C32C32C30(17)

513 509 m 1.53 δQRing(49), δCCC II (13)

486 491 w 477 w 4.36 τCCCC I(58), γ C25C11C12C10 (17)

457 464 w 6.17 δCCC III(39), τCCCC II (12),δQRing(11)

445 9.44 τCCCC II(35), τC1C2C3N22(11),τC23C2C3C4(11), τCCCC I (10)

438 432 w 17.50 δN26C28N27(24), δC32C28C30(13),δC31C28C30(13)

424 0.36 τCCCC III (76)

413 0.22 τCCCC I (81)

401 400 w 398 w 2.50 τCCCC II(14), τCCCC III (14),γ F40C33C35C37(14), τN26N27C28H29 (10), τN26N27C28C30(10)

377 391 w 6.25 δCFC III (34), δC2O24C23(15),δN26O24C23(15), δC23N27N26(12),δC25N27N26(12)

356 358 w 6.13 δCFC III(23), τCCCC II (10),δC11C25C10(10)

323 0.91 τCCCC II (20), γ N27C23C25N26(11)

312 312 w 12.97 γ N27C23C25N26(35), γ C28C32C31C30(10), τCCCC II (10)

283 276 w 3.78 τCCCC I (16), δQRing(11)

266 257 w 0.21 υC10C25(20), δCCC I (39)

219 220 w 1.05 δCCC III(11), τ Qring(11), τCCCCI(10)

214 0.63 δC11C25C10(14), δC12C25C10(14)

192 181 w 3.84 τCCCC III (26), τ N27C28CC(18), τH29C28CC (18),τC25N26N27C28(17), τN27C23C25N26(15)

173 167 w 1.91 τC1C2C3N22(20), τC23C2C3C4(20),τC23N26N27C28(10),τC25N26N27C28(10), τN26N27C28H29(10)

149 0.84 δC23N27N26(15), δC25N27N26(15)

128 0.36 τQRing(28)

89 92 s 1.36 δN22C10C25(20), δN26C10C25(20), τN27C28C30C31(12), τ H29C28C30C31(12)

78 3.81 τ QRing(12), τCCCC III(10),τCCC25N22(10), τCCC25N26(10)

53 0.95 τCCC25N22(48), τCCC25N26(48)

52 0.14 τQRing(21), τCCC25N22(16),τCCC25N26(16)

37 0.02 τCCC25N22(18), τCCC25N26(18),δNC10C25(14), δN27C30C28(14),δN27H29C28(14), δN26C28N27(11)

30 1.18 τCNNC(46), τQRing(12)

23 0.12 γ N27C23C25N26(19),τC11C10C25N(17),τCNNC(17), τ QRing(11)

υ , stretching; δ, in-plane bending; γ , out-of-plane bending; τ , torsion; s, strong; m, medium; w, weak; v, very; br, broad. Mono-, ortho- andpara-substituted phenyl rings are designated as PhI, PhII and PhIII. QRing stands for quinazoline ring.a PED, potential energy distribution, only contribution larger than 10% were given.


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vibrations are observed at 991, 922, 755 cm−1 in the IR spectrum,966, 924, 852, 748 cm−1 in the Raman spectrum for ring PhI;1000, 973, 891 cm−1 in the IR spectrum, 886 cm−1 in the Ramanspectrum for ring PhII; and at 982, 841 cm−1 in the IR spectrum andat 818 cm−1 in the Raman spectrum for ring PhIII. The strong γ CHoccurring at 840 ± 50 cm−1 is typical for 1,4-disubstitution, andthe band observed at 841 cm−1 in the IR spectrum is assigned tothis mode. The DFT calculations give this mode at 837 cm−1. The IRbands in the 1729–2873 cm−1 region and their large broadeningsupport the intramolecular hydrogen bonding.[59]

Geometrical parameters and first hyperpolarizability

To best of our knowledge, no X-ray crystallographic data ofthis molecule have yet been established. However, the the-oretical results obtained are almost comparable with the re-ported structural parameters of the parent quinazoline molecules.Gai et al.[60] reported C23 –N26, C25 –N26, C3 –N22, C2 –C23 andC3 –C2, as 1.3703, 1.4623, 1.4043, 1.4823 and 1.3903 Å, re-spectively, for a quinazoline derivative. In the present case,the corresponding values are 1.4268, 1.4204, 1.3902, 1.4590and 1.4125 Å. For the title compound, the DFT calculationsgive the bond angles C23 –N26 –N27 = 124.0◦, C23 –N26 –C25 =121.2◦, N27 –N26 –C25 = 114.3◦, O24 –C23 –N26 = 121.3◦,O24 –C23 –C2 = 123.5◦, N26 –C23 –C2 = 115.2◦, C3 –C2 –C1 =120.3◦, C3 –C2 –C23 = 119.6◦, C1 –C2 –C23 = 120.2◦, C2 –C3 –C4 =119.5◦, C2 –C3 –N22 = 121.3◦ and C4 –C3 –N22 = 119.2◦, whereasthe corresponding reported values[60] are 120.3, 121.0, 118.0, 121.8,122.7, 115,5, 119.7, 120.6, 119.6, 120.0, 118.6 and 121.2◦.

For another quinazoline derivative, Costa et al.[61] reportedthe bond lengths C3 –N22 = 1.3954, C25 –N26 = 1.3904 andC23 –N26 = 1.4174 Å, while in our case these bond lengthsare 1.3902, 1.4204 and 1.4268, respectively. The dihedral anglesC1 –C2 –C23 –N26 and C23 –N26 –C25 –C10 are 177.5 and 172.7◦. Thisindicates that the Ph ring II and the quinazoline moiety of thetitle compound are in tilted positions. Also, the dihedral anglesC13 –C11 –C10 –C25, C10 –C25 –N22 –C3 and C10 –C25 –N26 –C23 are−175.2, −177.5 and 172.7◦, respectively, which shows the Ph Iring and the quinazoline moiety are in different planes.

The experimental N–N bond length of hydrazine[62] is reportedas 1.449 Å and the electron diffraction N–N bond length oftetramethyl hydrazines[63] is reported at 1.401 Å.

Kostava et al.[64] calculated the N26 –N27 bond lengths of3,5-pyrazoledicarboxylic acid (H3pdc) molecules with differentmethods and found the bond lengths varying from 1.318to 1.357 Å; in the present case, the N26 –N27 bond length is1.4033 Å, which somewhere between the length of an N–N singlebond (1.45 Å) and an N=N double bond (1.25 Å). Both of theC25 –N22 = 1.3078 Å and C23 –O24 = 1.2535 Å bonds show typicaldouble bond characteristics. However, the C3 –N22 bond length(1.3902 Å) is shorter than the normal C–N single bond lengthof about 1.48 Å. The shortening of the C–N bond reveals theeffects of resonance in this part of the molecule.[65] Accordingto Gai et al.,[60] the bond angles C23 –N26 –N27, C23 –N26 –C25 andN27 –N26 –C25, are 120.3, 121.0 and 118.0◦, while in the presentcase these angles are 124.0, 121.2 and 114.3◦. For a quinazolinederivative[66] Krishnakumar and Muthunatesan[66] reported thebond lengths N22 –C25, C25 –N26, C23 –C2, C2 –C1, C1 –C6, C6 –C5,C5 –C4 and C4 –C3 as 1.311, 1.362, 1.427, 1.414, 1.380, 1.415,1.380 and 1.416 Å. In the present study, the corresponding valuesare 1.3078, 1.4204, 1.3902, 1.4081, 1.3896, 1.4116, 1.3893 and1.4094 Å. The DFT calculations give the bond angles N22 –C25 –N26,

C25 –N26 –C23, N26 –C23 –C2, C23 –C2 –C1, C2 –C1 –C6, C1 –C6 –C5,C6 –C5 –C4 and C5-C4-C3 as 121.9, 121.2, 115.2, 120.2, 119.7,120.1, 120.6 and 119.8◦, whereas the corresponding reportedvalues are 127.7, 116.2, 123.4, 124.7, 119.5, 120.3, 120.9 and120.1◦, respectively. The N27 = C28 moiety is essentially planaras seen from the torsion angles N27 –C28 –C30 –C32 = 178.9◦

and N27 –C28 –C30 –C31 = – 1.0◦. The N22 –C25 ring moiety isslightly twisted from the phenyl ring II (C2 –C3 –N22 –C25 = 3.1◦,C4 –C3 –N22 –C25 = −178.4◦) and more twisted from the phenylring I (N22 –C25 –C10 –C11 = 139.3◦, N22 –C25 –C10 –C12 = – 35.2◦),as is evident from the torsions angles. The differences betweenthe lengths of CN bonds are similar to the values of reportedquinazoline derivatives,[67] and this situation can be attributed tothe difference in hybridization of the adjacent carbon atoms.

Fluorine is highly electronegative and tries to obtain additionalelectron density and attempts to draw the electron density fromthe neighboring atoms, which move closer together in order toshare the remaining electrons more easily as a result. Because ofthis, the bond angle A(35,37,33) is found to be 122.7◦ and theexocyclic angles A(33,37,40) and A(35,37,40) become 118.6◦ and118.7◦, respectively.

Analysis of organic molecules having conjugated π -electronsystems and large hyperpolarizability using infrared and Ramanspectroscopy has evolved as a subject of research.[68] The potentialapplications of the title compound in the field of nonlinear opticsdemands the investigation of its structural and bonding featurescontributing to the hyperpolarizability enhancement, by analyzingthe vibrational modes using the IR and Raman spectra. The ring-stretching bands at 1645, 1604, 1511, 1451, 1409 and 1318 cm−1

observed in IR have their counterparts in Raman at 1636, 1604,1511, 1450, 1416 and 1318 cm−1, respectively, and their relativeintensities in IR and Raman spectra are comparable.

The first hyperpolarizability (β0) of this novel molecular systemis calculated using HF/6-31G∗ basis set, based on the finitefield approach. In the presence of an applied electric field, theenergy of a system is a function of the electric field. The firsthyperpolarizability is a third-rank tensor that can be described bya 3 × 3 × 3 matrix. The 27 components of the 3D matrix can bereduced to 10 components because of the Kleinman symmetry.[69]

The components of β are defined as the coefficients in theTaylor series expansion of the energy in the external electric field.When the electric field is weak and homogeneous, this expansionbecomes

E = E0 −∑

i

µiFi − 1

2

∑ij

αijFiFj − 1

6

∑ijk

β ijkFiFjFk

− 1

24

∑ijkl

γ ijklFiFjFk Fl + . . .

where E0 is the energy of the unperturbed molecule, Fi is thefield at the origin, µi , αij , β ijk and γ ijkl are the componentsof dipole moment, polarizability, the first hyperpolarizabilitiesand second hyperpolarizibilites, respectively. The calculated firsthyperpolarizability of the title compound is 2.445 × 10−30 esu(Table S2, Supporting Information), which is comparable withthe reported values of similar quinazoline derivatives,[70] butexperimental evaluation of this data is not readily available. Weconclude that the title compound is an attractive object for futurestudies of nonlinear optical properties.

In order to investigate the performance and vibrationalwavenumbers of the title compound, the root mean square


53

5


Figure 4. Correlation Graph. This figure is available in colour online at www.interscience.wiley.com/journal/jrs.

value (RMS) and correlation coefficient between calculated andobserved wavenumbers were calculated (Fig. 4). The RMS valuesof wavenumbers were evaluated using the expression[71]:

RMS =√√√√ 1

n − 1

n∑i

(υcalci − υ

expi )2

The RMS error of the observed Raman bands is 12.95 and thatfor IR bands is 21.15.

Conclusion

The FT-IR and FT-Raman spectra of 3-{[(4-fluorophenyl) methy-lene]amino} -2-phenyl quinazolin-4(3H)-one were studied. Themolecular geometry and the wavenumbers were calculated usingB3LYP/6-31G∗ basis and the normal modes are assigned by PEDcalculations. The simultaneous IR and Raman activation of the C=Ostretching modes shows the charge transfer interaction through aπ -conjugated path. Optimized geometrical parameters of the titlecompound are in agreement with the reported values. Analysisof the phenyl ring modes shows that C–C stretching mode isequally active as strong bands in both IR and Raman, which canbe interpreted as the evidence of intramolecular charge transfervia conjugated ring path and is responsible for hyperpolarizabilityenhancement leading to non-linear optical (NLO) activity.

Supporting information

Supporting information may be found in the online version of thisarticle.

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