Chavan, H

Hanker, P P

Pattar, R R

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Indian J. Phys. 75A (3). 273-275 (2001)U Pan international lournalX-ray diffraction studies of 2-[2’-hydroxy salicylidene 5'-(2"-thiazolylazo)]benzoic acidS S Chavan, P P Hankarc*, A H jtagtap and R T PaUarDepartment of Chemistry, Si|tvaii University,Kolhapur-416 004. Maharashtra, IndiaE-mail . saniaycha2#yahoo com R e c e iv e d  J 8  J u l y  2 0 0 0 , a c c e p t ^  15  J a n u a r y  2 0 0 1Abstract The ligand 2-[2’hydroxy salicylidene 5'-(2”-thia/o!ylazo)] benzoic acid was synthesized by condensing 5-(2’-thiazolyla/o) salicylidehyde iind 2-amino benzoic acid. The purified sample has been subjected to the X-ray diffraciometry to elucidate structural information The structure of the sample IS found to be tetragonal belonging to non-primitive system The strain broadening effects are also examined and discus.scdKeywords • Azo compound, X ray diffraction.PACS No. : 61 10 N?Thiazolc derivatives have attracted considerable attention by rhemists since many of them have been used in medicinal ihcrapy [1,2). Derivatives of thaizole have been widely used as antibacterial f3], antifungal [4], anticancer [5] and anthelmintic16] 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 co-ordinating behaviour of ligands containing this important functional group, wc have synthesized one such hgand 2-[2-hydroxy salicylidene5'-(2"thiazolylazo)] benzoic acid and examined for structural properties.All the chemicals used were of AR grade. 5-(2’-thiazolylazo) salicylaldehyde was prepared by diazotisation of 2 aminothiazole (1 g, 0.01 mole) using cone. HCl and NaN02 following the method feported earlier [7]. The diazotised solution so formed was consequently coupled with salicylaldehyde (1.28 g, 0.01 mole) dissolved in 15 ml of aqueous 2 N NaOH. The reaction mixture was stirred for 1 h at 0”C and then allowed to warm slowly at room temperature. The brown precipitate formed was filtered, Washed with water and recrystallised from ethanol.5-(2’-thiazolyIazo) salicylaldehye (5g, 0.02 mole) was dissolved in ethanol (100 cm*^ ) to this, a solution of 2-amino benzoic acid (2.939 g, 0,02 mole) in ethanol ( 10 cm^) was added and resulting mixture was refluxed for 3-4h on water bath. AfterC orresponding Author.cooling the solution was poured in ice-cold water, the separated solid was filtered , dried and purified by repetitive rccrystallisation with ethanol. The purity of the product was checked by TLC (Thin layer chromatography).Colour, yield, melting point and elemental analysis are as follows :Brick red, yield 60%, M p.-137«C, IR -1619 cm~’ ( i' C = N), 1589 -  cm"‘ (V N = N), 1281 cm' ‘ (v C-O). Anal. Cald. for C ,7 H,2N p^S, C: 57.94%, H: 3.43% N: 15.89% foundC: 56.74%, H:3.46%r,N: 16.09%.Structure of the ligand was tentatively fixed as given in Figure 1 on the basis of elemental analysis, IR, UV and ’HNMR spectral studies.A N =  N oHIC : OH COOHFigure 1. Structure of ligand.The XRD (X-ray diffraction) spectra were recorded on Phillips PW 3710 diffractometer attached to a digitized computer alongwith graphical assembly in which CuKa radiation source connected with the tube Cu-Ni 25 kV/20 mA was used.©2001 lACSI I274 5 S Chavan, P P Hankare, A H Jagtap and R T PattarITic X-ray diffraclogramme of 2-[2’ hydroxy salicylidene 5'-(2" thiazolylazo)] benzoic acid (Figure 2) records twenty one reflections between and lOO*' (2^) with maxima at 26 = 27.165^ ’ corresponding to a value ofd=  3.280 A.The experimental density was determined by using specitie gravity method. Which further enabled to calculate the volume of unit cell. The number of atoms per unit cell n were calculaied by using the equation (p = nM / NV) and was found to he 2 With this number, the theoretical density was fixed. The otherTable 2. X-ray parameters of 2-[2'-hydroxy salicylidene thiazolylazo)] benzoic acid.The indexing of the spectrogram with respect to the prominent peaks have been carried out by using computer software and trial and error methods [8]. The programme was modified in such a way that a good fit could be obtained between observed and calculated d and Q values and having symmetry constraints. The method also yielded hkl (miller indices) values. The relative intensities corresponding to the prominent peaks have been calculated (Table 1).Structure TetragonalSpace group 14/mmmLauc group 4/mPoint group 4/mmmSymmetry of lattice Non primitiveLattice parameters IV 612 A14.V07 ABond angles «  = /} = y = 90"Vol of unit cell 5733.69 A'Radius of atom 8 492 AVol of atom 2565 18 A'Packing fraction 44.74%Density P (Experimental) 0 184 gr/cc(Theoretical) 0 204 gr/ccPore fraction 27 43%Thickness of particle 257 61 ATable 1. Powder X-ray diffraction data of 2-(2'-hydroxy salicylidene 5'-(2"-lhiazoIyla/o)| benzoic acidPeakNo.2 0  degA AQ,.. 0... hkl Rl%SyxIO''1. 12.010 7.363 7.454 0.0184 0.0180 002 5 3 2 002. 13.410 6.597 6.565 0 0230 0 0232 112 95,5 2 003. 14.165 6 247 6 287 0.0256 0 0253 221 16 2 2 004. 17 525 5.056 5 077 0 0391 0.0388 222 28 8 2 005. 18 390 4.820 4 817 0.04 m 0 0431 013 26 0 2 006, 20.290 4 373 4.385 0 0523 0.0520 240 5.3 3.007. 22.195 4.001 4.010 0.0624 0.0622 142 26 4 3,008 24.355 3 651 3 661 0.0750 0 0746 014 1 1 9 3.009. 25.200 3.531 3.538 0.0802 0.0799 251 10.1 3.0010. 25.920 3.434 3.436 0.0848 0.0847 143 14.4 3.0011. 27.165 3.280 3 281 0.0930 0.0929 351 100 0 3.0012 28 630 3 115 3 101 0.1030 0.1040 260 17 1 4.0013. 31.625 2.826 2 823 0 1251 0.1255 125 9.6 4.0014. 33.030 2.709 2.705 0.1362 0.1367 163 2 5 4.001.^ . 38.375 2.343 2.349 0 1821 0.1813 281 8.7 5 0016. 41.985 2.150 2.149 0.2163 0.2165 265 1.7 5.0017. 43.625 2.073 2.072 0.2327 0.2329 573 2.3 5.0018. 44.165 2.029 2.031 0.2428 0.2425 175 19.1 5,0019, 51.195 1.782 1.784 0.3146 0.3141 067 1 9 6.0020. 64.925 1.435 1.438 0.4856 0.4838 2310 3.5 7.0021. 78.045 1.223 1.225 0.6681 0,6661 1049 2.3 7 00X-ray diffraction studies of 2-lT-hydroxy salicylidene 5'-(2"-tliiazolylazo)J benzoic acid 275parameters such as pore  fraction , pack ing  fraction , particle size, radius o f atom  w ere then  calcu lated . Space g roup  and po in t group o f the ligand  w ere no ted  from  In ternational Table for X ray cry.stallography [9). A ll these values are p resen ted  in Table 2.Com parison o f  the value o f  d and Q reveals a good agreem ent between the ca lcu la ted  and observed  va lues o f  d and Q, on the basis of assum ption  o f  te tragonal structure . T he  structure yields values for lattice constan ts  and cell vo lum e as a  = /? 19.612 A, (■:z 14.907 A an d  V = 5733 .69A '^  respectively. T hese values were further refined by using  w eigh t frac tion  m ethod . The refined parameters w ere used fo r find ing  ou t Space g roup  and L aue group. In con junction  w ith  such cell param eters , the condition110,111 such as a  =  f  and a  =  =  y  =  9 0 ” requ ired  for the sample to be tetragonal w ere tested  and found to  be satisfactory. Hence, it is concluded  that the  structu re  o f  the p resen t ligand is tetragonal.0.4 0 6sineFigure 3. Analysis of homogeneity.T he partic le  size o f the sam ple w as calcu lated  by using an equation  t = 0.9 XI B cos 0 . The.se param eters can d istinguish  betw een natural particle size and particle size due to broadening effect. T his w as done by calcu lating  fu llw idlh at ha lf m axim um  (B) corresponding  to its B ragg 's () and thereby com puting cos and sin values. The nature  and behav io r o f these values for the presen t ligand are show n graphically  in F igure 3.A  plot o f B cos 6 versus sin 9 w as found to  be a .straight line, parallel to X axis indicating an ab.sencc o f any strains caused by in h o m o g e n e o u s  la ttic e  d is to r t io n s  and c o m p o s itio n a l flu i|tuations. H ence, prc.scnt sam ple seem s to be hom ogeneous w it|i respect to the partic le  size dcstribulion.\K e 4  f e n c e s[1 ] M Akabar Ali and S E Livingstone C o o r d in a t io n  C h e m  R e v  13 101 (1974)[11 R J Sundberg and R B Marlin C h e m  R e v  74 471 (1974)[3] N H Bhavsar, A V Kasture and K R I)esai A s ia n  J  C h em  11 16^  (1999)[4] S G Wadodkai and A V Kasture J  In d ia n  C h e m  S m  61 374(1984)[51 H C Gcrg and R A Sharma J  P h a r m  S o i 59 348 (1970)[6] B C Sharma H u ll C h e m , S o c  J p n  40 2422 (1967)[7] H H Hovind T h e  A n a l  R e v  100 769 (1975)[8] R T Pattar, K R Choukimath and V G Tulasigiri In d ia n  J  P h w  73A 343 (1999)19) J D H Donney and David Maker T ab les  o f  S p a c e  G ro u p  C riter ia , C r y s ta l lo ^ r a p h u p ie s  N a tu r a l i s t  C a n a d ie n  67 33 and 160 (1940)[10] B D CullUy E le m e n ts  o f  X - r a \  D i f f ia i  turn (Massachusetts Addison - Wesley) (1956)111] MS Reiser, H P Ruokshy, A J C Wilson X - r a y  D i f f t a i t t o n  b y  P o l y i r y s ta l l i n e  M a te r ia l (Institute of Physics, London) (1956)

X-Ray Diffraction Studies of 2-[2’-Hydroxy Salicylidene 5'-(2"-Thiazolylazo)] Benzoic Acid

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X-Ray Diffraction Studies of 2-[2’-Hydroxy Salicylidene 5'-(2"-Thiazolylazo)] Benzoic Acid

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