Battase, P S

Gavali, L V

Hankare, P P

Jagtap, A H

Naravane, S R

IACS Institutional Repository

C l'4 'o te^  \  IJP> >X-ray diffraction studies of 8-(-2-azothiazolyl-)-7-hydroxy 4-methyl coumarinP P Hankare*, A H Jagtap, L V Gavali, P S Battase and S R NaravaneD e p a r tm e n t o f  C h em is try ; S h iva ji U n iversity  K o lh a p u r '4 1 6  0 0 4 , M a h ara sh tra , IndiaE-mail • p_,hankare(|Tcdiffmail com  R eceived 8 May 2003, at^epted 28 July 2003A bstract ‘ L igand  8 -(-2 -a z o th ia z o ly I- ) -7  h y d ro x y  4 -m e th y l co u m arin  w as sy n thesized  by co n d en s in g  2 -am in o th iaz o lc  and  7 -h y d m x y  4 -m eth y l coumarin Purified sam ple  has b een  su b jec ted  to  X -ray  d iffrac tio n  to  e luc ida te  structural in fo rm ation  S truc tu re  o f  the sam ple  is found to  be tetragonal belonging non-prim itive  system . S tra in  b ro ad en in g  e ffe c ts  are  a lso  exam ined  and  d iscussedK eywords ■ X-ray d if fra c tio n , azo  s u b s titu te d  co u m arin , s tra in  b roaden ing .P \C S  N o . . 6 1 .1 0 .N zCoumarin compounds are found to be of great importance due to their fascinating useful properties like fluorescence, biological activity, coordinating abilities etc. Coumarin derivatives have been found to exhibit antibiotic, anti fungal, anticoagulatmg and plant growth regulating properties U “3]- Azo coumarins were recommended as potential carcinostats [4). Thiazolyl azocoumarins show antifungal antibacterial activities along with lluroscence properties [5,6].Thiazole derivatives have attracted considerable attention by Chemists since many of them have been used in medicinal therapy [7,8]. Derivatives of thiazole have been widely used as antibacterial [9],antifungal | lOJ, anticancer [11] and antihelmintic112] agents. It is known that the activity of many enzymes depends upon the interaction of thiazole group with transition metal ion. It is therefore of considerable interest and importance to know the detail about coordinating behaviour of ligands t^ ontaining this important functional group, we have synthesized one such ligand 8-(-2 azothiazolyl-) 7-hydroxy 4-methyl coumarin and examined for structural properties.All chemicals used were of AR grade. Ligand was prepared bydiazotisationof2-aminothiazole(lg,0.01 mole) using cone. HCi and NaN02 following the method reported earlier [13] and ‘Consequently coupled with 7-hydroxy 4- methyl coumarin (1.76g,  ^01 mole) dissolved in 15 ml of aqueous 2N NaOH. Reaction •fixture was stirred for 1 h at 0°C and then allowed to warmslowly at room temperature. Brick red precipitate formed was filtered, washed with water and recrystallised from ethanol. Purity of the product was checked by TLC (Thin layer chromatography).Colour, yield, melting point and elemental analysis are as follows:Brick red, yield 72%, M.P.- 189°CUV-39370 cm * and 44843 cm* ^  71* organic moiety), 30487 cm* { n - n *  of C = O group) and 23310 cm * (- N = N-), IR- 3478 cm * (v OH), 1625 cm"* V (N = N), Thiazole viabration [1377 cm * (C = N), 1459 cm * (C = S)], 1678 cm * [v(C = 0)j, 1212 cm’* v(C = 0).C,3HAN3S.C:54.34%,H:3.15%N: 14.62%),S:11.16%foundC: 55'l0%»,H:3.27,N: 14.37%,S: 10.97%.Structure of the ligand was tentatively fixed as given in Figure 1 on the basis of elemental analysis, IR, UV and 'HNMR spectral studies.'c«orresponding A u th o r F ig u re  1. S tru c tu re  o f  ligand.©20041ACS382 P P Hankare, A H Jagtap. L V Gavali, P S Battase and S R NaravaneXRD (X-ray diffraction) spectra were recorded on Philips PW 3710 diffractometer attached to a digitized computer alongwith graphical assembly in which CuK a radiation source connected with tube Cu-Ni 25 kV/20 mA was used.X-ray diffractogram of 8-(-2-azothiazolyl-)-7-hydroxy 4- mcthyl coumarin is shown in Figure 2. The XRD pattern shows fourteen reflections between 10" and 100" (20) with maxima at 20 = 26.75" corresponding to a value of d -  3.3305 A .F ig u r e  2 . X -ra y  d if f ra c to g ra m  o f  L ig a n dIndexing of spectrogram with respect to the prominent peaks have been carried out by using computer software which uses an interactive method for analysis of powder diffraction data and having indexing program of version 2.3 named as Powdmult, prepared by E.Wu of School of Physical Sciences, Flinder University of South Australia.The indexing is confirmed on the basis of correction obtained between observed and calculated d  and Q values and having symmetry constraints [14]. This method also yielded hkl (miller indices) values. Relative intensities corresponding to the prominent peaks have been calculated (Table 1).T a b le  1. X R D  d a ta  o f  8 - ( -2  a z o th ia z o ly l - )  -7  h y d ro x y  4 -  m e th y l c o u m a r in .P e a kN o .2 0  d e g re ed  (A ) d  (A )o b se rv e d  c a lcu la tedQoh.1h k 1 RI (%)1 1 1 .2 5 7 .8 5 8 6 7 .8 5 8 6 0 .0 1 6 2 0 .0 1 6 2 0 0 3 3 7 .52 1 3 .8 2 6 .4 0 2 5 6 4 0 2 5 0 .0 2 4 3 0 .0 2 4 3 1 0 1 5 143 1 7 .4 5 5 .0 1 8 0 5 .0 7 7 5 0 .0 3 9 7 0 .0 3 8 7 1 0 3 3 3 .14 1 9 .2 2 4 .5 9 6 3 4 .6 1 3 1 0 .0 4 7 8 0 .0 4 6 9 1 1 1 1 1  15 2 4 .1 9 3 .5 6 7 3 3 .6 7 6 6 0 .0 7 8 5 0 .0 7 3 9 I 1 1 1 4 .76 2 6 .7 5 3 .3 3 0 5 3 .3 3 0 2 0 .0 9 0 1 0 .0 9 0 2 I 1 5 1 0 07 2 7 .8 5 3 .1 9 3 5 3 .2 0 1 3 0 .0 9 8 0 0 .0 9 7 5 2 0 2 3 3 .58 2 9 .7 1 2 .9 9 5 2 3 .0 0 4 8 0 .1 1 1 4 0 .1 1 0 7 1 0 7 2 4 .39 3 2 .1 4 2 .8 0 1 8 2 .7 8 2 4 0 .1 2 7 3 0 .1 2 9 1 2 1 3 7 .1 41 0 3 8 .4 3 2 .3 4 4 3 2 .3 4 0 4 0 .1 8 1 9 0 .1 8 2 5 2 2 1 7 .5 71 1 3 9 .0 2 2 .3 0 0 5 2 .3 0 6 6 0 .1 8 8 9 0 .1 8 7 9 2 2 2 1 1 .31 2 4 0 .6 5 2 .2 1 8 4 2 .2 1 7 5 0 .2 0 3 1 0 .2 0 3 3 3 0 0 1 0. 813 4 3 .5 7 2 .0 8 2 8 2 .0 7 5 5 0 .2 3 0 6 0 .2 3 2 1 3 0 4 1 5 .714 4 8 .2 6 1 .8 8 7 7 1 .8 8 4 2 0 .2 8 0 6 0 .2 8 1 6 1 0 1 2 5 .5 9Experimental density was determined by using specifi^ .^ gravity method which further enabled to calculate volume unit cell. Number of atoms per unit cell n was calculated b\ using the equation (p = nM/NV) and was found to be 2 Wn^  this number, theoretical density was fixed.Other parameters such as pore fraction, packing fraction particle size, radius of atom were then calculated. Space giou^ , and point group of ligand were noted from International Tahj^  for X-ray crystallography [ 15]. All these values are presenicd m Table 2.T a b le  2. X -ray  p a ram e te rs  o f  8 - c o u m a r in .(-2  a z o th ia z o ly l- )  -7  hydroxy 4 imiivS tru c tu re T e tra g o n a lS pace  g ro u p 1 4 /m m mL aue g ro u p 4 /mP o in t g ro u p 4 /m m mS y m m e try  o f  la t t ic e N o n  p rim itiv eL a ttic e  p a r a m e te r s fl =  b  = 6 6525 Ac  = 23  5758  AB ond  an g les 0  =  ^  =  7 =  <j()“Vol o f  u n it ce ll 1 0 4 3 ,3 7  A 'D e n s ity  p  ( E x p e r im e n ta l) 0 ,4 5 7 1  g t/c cD e n s ity  p  ( T h e o re t ic a l) 0  4 4 5 6  g r/ceP o re  f r a c tio n 0  0 2 5  1T h ic k n e s s  o f  p a r t ic le 232  AComparison of the value of d  and Q reveals a good a g re e m e n t between the calculated and observed values of d and (), on (he basis of assumption of tetragonal structure. Struciurc yields values for lattice constants and cell volume asa = h -  6.6525 A,. = 23.5758 A and V= 1043.37 AVespeclivciy. These values wcie further refined by using weight fraction method. R e f in e d  parameters were used for finding out Space group and L ane  group. In conjunction with such cell parameters, the condition [ 16,17] such as a = c and a  = /S = y = 90" required for ihc sample to be tetragonal were tested and found to be satisfacior> Hence, it is concluded that structure of the present ligand i^  tetragonal.Particle size of the sample was calculated by using an equation / = 0.9 A / c o s0 . These parameters can distinguish between natural particle size and particle size due to broadening effect [18]. This was done by calculating full width at hail maximum (B) corresponding to its Bragg's 0 and thcrcbv computing cos and sin values.The nature and behaviour of these values for present ligand are shown graphically in Figure 3. A plot of parameter B cosO against sin 0 was observed to be a straight line parallel to (i.e, x) axis indicating an absence o f any strains caused bv inhom ogeneous la ttice  d is to rtio n s and compositionalX-ray diffraction studies of 8-{-2-azothiazolyl-)-7-hydroxy 4-inethyl couinarin 3 8 3tions. Hence, present sample seems to be homogeneous luh respect to the particle size distribution.Figure 3. Analysis of Homogeneity.References[ 1 1  B Kalluraya, A M Shoney and Shalini Isdoor Indian J lU ie w iy d k  Chem 11(2) 59(2001)12] El Sayed, A M Allah and D A Abd Phosphours Sulphur Silicon and Related Elements 170 75 (2001)1 3 ) AM Mandour, M Ahmed, M I Nassar and Z Ba//a Egypt J Pliarm Sri 36 71 (1995)f4| V S Jolly and J P N Singh7 Indian Chem Sor IV lll 527 (1989)15] A El Ansary, E M Abbas and M M Omav Kolorisztikai Ertesitia 6 lf)4 (1087)16) B Kalluraya. P V Iskuir and Rai B (ianeith J. Indian Council of Chemists 16 26 (1999)[7] M Akabar All and S E Living,stonc Coordination Chem. Rev 13 101 (1974)[8] R J Sundberg and R B Martin Client Rev 74 471 (1974)(91 N H Hhav.sar. A V Kaslure and K R IX-sai A.uan J Chem. 11 165(1999)[10] S G Wadodkar and A V Kastuic J Indian Chem Sor. 61 374 (1984)f i l l  H (' Gerg and R A Sharma J Pharm Sor. 59 348 (1970)j[12] B C Shaima Bull Chem. Sor. Jpn 40 2422 (1%7),113] H H Hovind Tlw Anal Rev 100 769 (1975)' 1141 R T Pattar, K R Chowkimalh and V G Tulasigin Indian J Phy.\. 73A 343 (1999)[15] J D H Donney and David Maker Tables of Spare <S Group Criteria. Cry.stallographiques Naturalist Canadien 67 p33 and pi60 (1940)[ 161 B D Cullity Elements oj X-ray Diffraction (Massachuse((s ■ Addison - Wesley) (1956)[17] 11 S Peiscr, H P Rookshy, A J C Wilson X-ra\ Diffiartion by Polyrry.Ualline Material (London Institute of Physics) (1956)118] P P Hankarc, L V Gavali and S S Chavan Indian J Phys 76A 587( 2002)

X-Ray Diffraction Studies of 8-(-2-Azothiazolyl-)-7-Hydroxy 4-Methyl Coumarin

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X-Ray Diffraction Studies of 8-(-2-Azothiazolyl-)-7-Hydroxy 4-Methyl Coumarin

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