Kokila, M K

Kulkarni, Geetha M

Kulkarni, M V

Murthy, V N Narasimha

Puttaraja

Shivaprakash, N C

IACS Institutional Repository

Inoi,an I  Phy^ - 639-642 (2004) O '' fo tc§ UP >Structure of 1-cyano, l-carbethoxy*2-(3 ' inethoxy-4 '-hydroxy) phenyl ethyleneV N Narasimha Murthy, M K Kokila and I’uttaraja Deparlmeni o f Physics. Jnanabharathi t'ampiis. Bangalore Univeisily, Bangalore >^60 056, Kaitialaka. IruiiaN C Shivaprakash*iJepartincni of InstrumcnUUion, Ibdiaii Insiiiuie of Science,Bangalore 560 012, Kaiiialaka, IndiaGcctha M Kulkarni ai^  M V KulkarmDepartment o f ('hemistry, Karnataka Univeisily, Dharwad 5S0 003. Karnataka, India K-mail shiv(«^isu,iisc ernet in Received 2 September 200S, accepted 2S i'ehruatv 2004distract The title compound Nj has been taken up lor study as it shows non linear optical (NLO) piopertics with an electron^Mthdrawing group at one end and an electron donating group at the other, with an extended ct^njugation in between The crystal structure has been Jcioinuncil ai lomn temperature Needle like crystals of the compound ciystalli/es m monoclinic system, space group R2Jn with cell dimensions , - IU046(‘^ )A, h = 9 35I(4)A, r - l2 647t5)A, p  -  97 13(3)"’ and /  -  4 The stiucture was solved by direct method and leOned by fullmailix least- nlu.iKN method to a final R ~ 0 046 for 1993 observed reflections The molecule on the whole is almost planar, the methoxy group makes a dihedral ol 0 7" with planai phenyl ring The cjirbethoxy moiety forms an extended planar /ig /ag  chain with the neighboring atoms The molecules are Md by strong O-H, .O. T-H... O and ( ’-H N inter- and intia- molecular hydrogen bondsKt>words Phenyl ethylene. X-ray crystallographyl*VfS No. 61 10 -i^(m-ccnirosymmelric aromatic compounds Iike4-nitro-2-methyl aniline have been found useful to study their nonlinear optical I MO] studies! 1 K 4-ary lidenc pyridenes with hydroxyl groups also been reported as possib le nonlinear optical materials, lulling the present investigation, the com pound as a push-pull nriolecule with electron donating -OH and -O CH 3 groups o f  the phenyl ring and a two armed conjugated side chain possessing  ^yano(CN) and ester groups as electron withdrawing groups ^^ r^ijugated with arylidene m oiety expected to exhibit NLO  P*‘^’perties o f Secondary Harmonic Generators (SHG) activity, ^^ rder to ascertain the stereochem ical relationship o f  cyano carbethoxy groups attached to C l with the aromatic moiety  ^2 and lo discuss the role o f  O-H. , .0  interaction in stabilizing Pricking mode, the crystal structure o f  the title compound been .studied.^^ rresponding AuthorThe title compound was obtained by the reaction o f vanillin with ethyl cyanacelate using pipendenc as catalyst. Fquimolar quantities o f the reactants were allowed to stand at ice bath temperature for three hours in presence o f  catalytic quantities of piperidene. The reaction mixture was worked up according to the literature m cthod|2 J and crystallized by slow  evaporation technique using ethanol as solvent.Intensity data w ere m easured on Enraf-Nonius C A D 4  diffractom eter|3 | with graphite-monochromatt.sed, MoK^  ^radiation, (A = 0 .7107A). The data was corrected for Lorentz and polarization factor] 4). The crystal data o f the compound is given in Table I. The structure was solved by direct method and refined by full-matrix least-squares method using SI fELXI--97|5] program. Non-H atoms were refined with anisotropic thermal parameters. All hydrogen atoms have been geometrically fixed and refined for isotropic thermal parameters.©20041ACSTabiv640. Crystal data for the title compoundI*ale yellow, needle like C ,,H , ,0 ,N  247.24 / ’21/« rnonocliriic  a = 10 f)460)A,= 0 351 (4) A,r =. 12 647(5)AV N Narasimha Murtliy et alO ysta l morphology ( ’hemical toiniiihi Molecular weight ('lystal system  Space group ( ’ell consianisTable 2. The final positional and equivalent is(»iiopic ih- paramcters(A^) of non^hydrogen atoms with Estimated Standard l>c\ ” * (c s.d’s) in parenthesesVolumeNumber of formula unit Z Density (calculated)Density (measuicd)Absorption coefficient /i(MoK,^) Unique data measured Observed data with / ‘O > 4 a ( /•'()) /'(OOO)R/?w/( = 07 13(3)'  ^1240.2(X) A ’ 4I 315 gm/ce I 207 gm/cc 0 OOS ninr* 2447  1003 520 00  0 046  0 lOST he final p ositional and eq u ivalen t isotrop ic thermal parameters o f  non-hydrogen atoms are listed in Table 2. The anisotropic temperature factor for non-H atoms are presented in Table 3. The bond lengths, bond angles and torsion angles are given in Table 4. The chem ical diagram o f the m olecule is asAtom X V z I'lSOo i -0 2567(3) -0 5462(3) 1.0647(2) 0 07 ‘m0 2 -0 0824(2) -0 4130(3) 1 2009(2) 0 07 4^0 3 0.1779(2) 0.0477(3) 0 7753(2) 00 4 0.3157(2) 0 0988(3) 0 9198(2) 0 0 , -wN1 0.2434(3) -0 .0658(4) 1 1386(3) 0Cl 0 154.5(3) -0 .0640(3) 0 9401(2)C‘2 0 0546(3) -0 .1432(4) 0.8990(2) 0( 3 0 2055(3) -0 0646(4) 1 0506(3) 0 fi(M 0 2156(3) C) 0327(3) 0 8682(2) 0 Ofij;,C5 0 3807(4) 0.2010(5) 0 8582(3) (}C6 0 4796(4) 0 2731(6) 0 9319(4) 0 (>0l(..C l 0 0100(4) -0 3452(6) I 2751(3) 0 07^('1' -0 0234(3) -0 2457(3) 0.9468(2) {)('2* -0 .0097(3) -0 .2776(4) 1 05(32(2) n( ’3‘ -0 0872(3) -0 3764(3) 1 0961(2) 0 Or.D*C4’ -0 1804(3) -0 4481(3) 1 0277(3) 0C'5’ 0 1937(3) -0 4173(4) 0 9201(3) 0 irM'-CYi' -0 I 165(3) -0 3177(4) 0 8799(3) 0 0^ )'^  '-shown in Figure 1. AnORTEPlC] plot o f the molecule with < probability thermal ellipsoids, viewed down r/-a\is is shuviin Figure 2.Tabic 3. Anisotropic temperature factor(A ’) toi non-hydiogen atoms with e s d's in parenthesesAtom in  1 1/22 f/33 U23 (713 (/12O l 0 0 840(2 ) 0 .0 8 6 2 (2 ) 0 0703(2) -0 0068(1) 0 01 8 3 (1 ) -0 0186(1 )0 2 0 0810(2 ) 0 0852(2 ) 0 0579(1) 0 0069( 1) 0 0 0 8 7 (1 ) -0 0130(1 )0 3 0 .0 7 9 4 (1 ) 0 0866(2 ) 0 .0 5 8 5 (1 ) 0 0060( 1) 0 .0 1 9 5 (1 ) 0 0 001(1 )0 4 0 0720(1 ) 0 0804(2 ) 0 0677(1) 0 0()80( 1) 0 ,0 1 4 8 (1 ) -0 .0 0 6 6 (1 )NI 0 0980(2 ) 0 1250(3) 0 .0 7 1 7 (2 ) 0 .0205(2 ) -0 .0 1 6 1 (2 ) -0 .0 2 9 0 (2 )Cl 0 .0 6 1 6 (2 ) 0 .0 6 7 5 (2 ) 0 .0599(2 ) 0 0 0 14(1 ) 0 .0 1 4 9 (1 ) 0 .0 0 9 3 (1 )C2 0 0 665(2 ) 0 071 1(2) 0 0525(2 ) -0 0006(1 ) 0 .0 1 3 8 (1 ) 0 .0 0 9 4 (2 )C3 0 06 4 3 (2 ) 0 .0 8 1 0 (2 ) 0 0720(2 ) 0 0 1 12(2 ) 0 .0 0 5 9 (2 ) -0 .0 075(2 )C4 0 0 649(2 ) 0 .0 6 8 5 (2 ) 0 .0618(2 ) 0 .0 0 0 9 (1 ) 0 .0 1 8 5 (1 ) 0 .0 0 6 4 (1 )C5 0 .0 7 7 0 (2 ) 0 .0 8 2 0 (2 ) 0 0 750(2 ) 0 .0 0 0 0 (2 ) 0 .0 2 3 8 (2 ) -0 .0 0 5 2 (2 )C6 0 .0 7 8 0 (3 ) 0 .1 0 0 0 (3 ) 0 .0 9 7 0 (3 ) 0 0 050(3 ) 0 01 7 0 (2 ) -0 .0 1 2 0 (2 )C l 0 09 0 0 (3 ) 0 .0 9 6 0 (3 ) 0 0601(2 ) 0 .0 0 9 7 (2 ) -0 .0 0 0 1 (2 ) -0 0050(2 )c r 0 .0 6 1 8 (2 ) 0 0654(2 ) 0 .0 5 6 8 (2 ) -0 .0001(1 ) 0 .0 1 2 0 (1 ) 0 .0 0 5 7 (1 )c r 0 .0 6 3 0 (2 ) 0 .0 6 5 5 (2 ) 0 0587(2 ) -0 0043(1 ) 0 .0 0 5 3 (1 ) -0 .0002(1)c y 0 0 6 10(2 ) 0 0652(2 ) 0 0575(2) -0 .0005(1 ) 0 .0 1 2 5 (1 ) 0 .0 0 8 4 (1 )C4* 0 .0 6 2 9 (2 ) 0 .0 6 5 8 (2 ) 0 .0 6 7 5 (2 ) -0 .0073(1 ) 0 .0 1 5 6 (1 ) -0 .0 0 0 9 (1 )C5* 0 .0 6 8 6 (2 ) 0 .0 8 4 0 (2 ) 0 .0 6 1 9 (2 ) -0 .0 117(2 ) 0 .0 0 8 5 (2 ) -0 ,0 0 5 3 (2 )C6’ 0 .0 7 1 3 (2 ) 0 .0 8 1 0 (2 ) 0 .0 5 2 6 (2 ) -0 .0045(1 ) 0 .0 0 9 3 (1 ) 0 .0 0 1 7 (2 )Structure of l-cyano, I-carhethoxy-2-{3' methoxy-4' hydroxy) phenyl ethylene ()4Iuif 4 Bond length (A), bond angle (”) and torsion angle (")for non-Bond lm B “ *s,,l c r  1 ^47(4) 02-C 3' 1 3 63(4 ) 0 2 -C 7  1 422(5)05 ('4 1 202(4) 0 4 -C 4 1.330(4) 04 -C 5  1 461(4)M ( 3 1 120(4) C l -('2 1 .346(5) Cl-'C3 1 435(3), 1 C4 1 4S9(4) C2 c r 1 44 8 (4 ) C5-C6 1 479(6)iT-C6' 1 304(4) Cr-C2' l.40C (4) C 2- r.3' 1 376(4)1 40 3(4) C'4’-C5’ 1 381(4) C5‘. C6* 1 380(5)-- - ----Bond anglesi v - o i n 118.0(3) C 4-04  C5 1 16 5(3)124 O(^) C'2 C'l C4 118 9(3)n - c \ - r 4 117 1(3) c i-C 2 * c r 132 0(3)Ni-(’3^ri 178 6(4) (73-C4-04 125 1(3)0  ^ ( 4 Cl 123 3(3) 04-C’4-Cl 111 5(3)04 ('5-(Yi 108 0(3) C6'-Cr-C2’ 118 3(3)('6’-(T  C2 117 9(3) C2' r r - c 2 123 8(3)( 120.7(3) o i c y c T 125 0(3)o : ('3' ('4' 114 7(3) C2'-C3'C4' 120 3(3)Ol-C4‘ ('5’ 1 19 4(3) 01-C 4'-r3' 121 5(3)rS'-C'4’ C3’ 1 19 1(3) (Y)’-r 5 ’ C4’ 120 7(3)( 5’ (Y)'-Cr 120 9(3)torsion angles( 7-02 ( ’3' C2' -  0,4(5)('1 ( ’2 (Y'-C2* 3,4(5)(1 CJ-C2 CM' -  1 5(6)(’4 04 C5-C6 174.1(3)(’2Y’l (;4-C)3 2.5(5)(.’S C)4-('4-()3 2 4(5).CH,/|*''!!urc I. Chemical diagram of the molecule.The phenyl ring is planar with 0 1 and C2 atoms lying in the square planes while 0 2  and C l  lying below the plane by '’f'l(>(3)°and 0.015(5)° respectively. The bond lengths and bond “"gles in the phenyl ring are normal. The methoxy group at C3’ l^ ct'planar with the phenyl ring. The torsion angle C7-02-C3'- " 's -0.4(5)°. The angle C2'-C3'-02 is larger than the angle C4’- ‘ '02 by about 10°. This might be due to c is  orientation of the02 -C 7  bond and C2'-C3' bond about ('3 '-02  bond which causes repulsion between the atoms C2' and C 717|.H7aHgure 2. OK'I'hl* plot of the molecule with piobahility ellipsouls viewed down n-iwisThe two armed conjugated side chain posses a linear C-C = NjCl -  C3 ^ N 1 = 17S.6(4)' ) chain and zig zag ester groups. The bonds C 4~03= 1.202(4) A and C.3-N1 = I.J 36(5) A show distinct double and triple bond character respectively. The conformation o f CH(CN)COO(\H^ can be described by the torsion angles C 1 - C2-C r-C2' IS 3.4(5) and C 3  C 1 C 2  C 1' is 1.5(6). The U)rsion angle C4-C)4-C5-C6=174.1 (3) indicates anli-tx^ri planar relation between the carbonyl carbon and the methyl group, fhe mean planes o f  the ethyl carbonate group makes dihedral angle o f 6.30( 1)"" with the mean plane o f phenyl ring, 'fhe torsion angle C 2-C 1-C 4-03  is 2.5(5)'^. The C = O bond is svn  to the ester group about the C- O, the torsion angle C 5 -04 -C 4-03  is 2.4(5)'^.'rhe molecular packing of the molecule along h -a w s  is shown in Figure 3. The m olecules are stabilized by inlra- and inter- molecular hydrogen bondings. The oxygen atom 0 3  o f the ester group makes a strong intra- m olecular contacts w hile the hydrogen atom o f the OH group at C4' gives a strong inter- and intra- molecular hydrogen bondings. The hydrogen bondings are listed in Table 5.Figure 3. Packing diagram of the molecule viewed along /. -^axis642 V N Narasimha M u rth  et alTbble 5. Hydrogen bondings (A ,")D-H . .A D-H H . A D D-H AO l-H I' . .. 02' t) 751(47) 2 230(44) 2 678(04) 1 10 21(43)C2-H2 o y 0 977(32) 2 404(32) 2.804(04) 103 80(22)C2'-H2' .. N l' 0.885(28) 2.y>S(20) 3 402(05) 151 30(25)OI-HT . .03" 0 751(47) 2 170(50) 2 835(04) 146 38(47)C5-H5B ,, 02". 0 975(43) 2 503(42) 3 399(05) 143 83(32)Equivalent posilions (1) r, V. :(li) 1/2,- y - l / 2 ,  f : + 1 / 2  (ill) > + 1/2, -  V -  1/2, + c -  1/2References[1] D Pugh and J N Sherwood Chem Bril 24 544 (lOfiH)|2] J Zabicky J. Chem Sor. Pari I 683 (1961)[3] Enraf-Nonius CAD4 PC version I 2 Eniaf ,Netherlands) (1993)|4] (' K Fair Molen Enraf Nonius (Delft Netherlands) (|i)no,(5) (i M Sheldrick SUFJJ(L-97 Program for Solutum uml /r,-;,,,,,, ol C rysta l S ln ir tu re  (University of (iottingcn (ini,n (1997)|6J (; K Johnson ORTEP ()R N I.-^794  (Oak Rid!.';i' Laboratory, Tennesse) (1965)17] M K Kokila, Puttaiaja, M V Kulkarni and Sarala Tluni|>i i Cry\t. 051 330 (1995)

Structure of 1-Cyano, 1-Carbethoxy-2-(3' Methoxy-4'-Hydroxy) Phenyl Ethylene

http://arxiv.iacs.res.in:8080/jspui/bitstream/10821/7235/1/Structure%20of%201-Cyano%2c%20I%20-Carbethoxy-_By%20V%20N%20Narasimha%20Murthy.pdf

Structure of 1-Cyano, 1-Carbethoxy-2-(3' Methoxy-4'-Hydroxy) Phenyl Ethylene

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