Dinesh, Rajnikant

Sharma, Bandhan

Varghese, Babu

IACS Institutional Repository

Indian J. Phys. 79 (1). 73-75 (2005) c s A ^ to e%$  U P  ^X-ray structural analysis of IH, 4Hfterahydroquinolizino-(9, 9a,lgh) coumarinRajnikant'", Dinesh*, M ousm |\ Babu Varghese- and Bandhan Sharma‘Condensed Matter Physics Group. IJnivcrstty o f Jammu. Jammu Tawi-180 006. India  ^ Regional Sophispicated Instrumentation C'cntre.Indian institute o f Te^hnology-600 008, Chennai, IndiaE-mail; rkaHtvcrma@icdiffniail comR eceived  26 March 2004, accepted  79 O ctober 2004A bstract The crystal structure o f IH,4H-terahydroquinolizino-(9. 9a, Igh) coumarin (CjjH,,NOj) has been determined by X-ray crystallographicit’chniques. The compound crystallizes in monoclinic space group P 2 /n  with n = 8 115(3). h ~ 19 067(10), c — 8.383(6) A. /I = 1 15 45(15)'*, Z ~ 4 The structure has been solved by direct methods and refined to reliability index of 5.99?>. The fused benzene and pyrone rings are planar. The piperidine ling (^  of the molecule adopts a distorted so/a  conformation whereas the piperidine ring f) exists in distorted chair conformation The crystal structure IS stabilized by inlcrmolecular C-H . O hydrogen bonds.K eyw ords ; Coumarin derivative, structure analysis, hydrogen bondsPACS N os. 6 1 .10 .N z, C l.5 0 .AhCoumarins exhibit a wide spectrum  of biological activity including antithrombotic and vasodilating effects on coronary vessels, a tonic influence on capillary blcx)d vessels, reduction in bl(H)d pressure, antispastic and photosensitizing effects [l]. They are found as heterosides in many dicotyledonous families, e.f>, Apiaceae, Asteraceae, Fabiaceae, Moraceae, Rosaceac, Ruhiaceae and Solanaceae [2J.Coumarins derivatives are efficient laser dyes in the blue and green region of the spectrum [3]. The mobility of the amino group reduces the fluorescence efficiency o f these dyes in polar solvents [3-5] but with a structurally rigid amino group, these derivatives show a high quantum yield o f fluorescence in polar solvents [5, 6]. X-ray studies of the title compound IH, 4H- tetrahydr<x)uinizilino-(9,9a, 1 gh) coumarin (1), have been carried out to determine its three-dimensional structure and also to understand the role of hydrogen bonding in the molecular packing. The chemical structure of this compound is shown in Figure 1.The title compoud was procured from Aldrich Chemical Company (U.S.A.) and its crystallization was tried with a variety of organic solvent systems. Good quality single crystals of (I) were grown using toluene as solvent. A white rectangular shaped* Corresponding Authorsingle crystal of (I) with dimensions 0.3 x 0.2 x 0.2 mm was mounted on an Enraf-Nonius CAD-4 diffractometer for automatic intensity data collection using M oK a radiation ( A = 0.71069F igu re 1. Chem ical structure o f  IH, 4H 'tetrahydroquiniziiino-(9, 9a, Igh) coumarin.A). The compound crystallizes in monoclinic space group P2j/n with unit cell parameters a  = 8.115(3) ,b = \ 9,067( 10), c = 8.383(6) A and = 115.45( 15)**. co /2 0  scan mode was employed for data collection with 0-range of 2 .1 4 -  24.96°. A total o f 2285 reflections were measured and out of which 2058 were found unique. Two standard reflections (3 2 1) and (1 0  3) measured after every 100 reflections and showed no significant variation in intensity. Reflection data were corrected for Lorentz and polarization effects and no absorption correction was applied.The structure was determ ined by direct m ethods using SHELXS86 software [7]. Full matrix least-squares refinement of02005IA C S7 4 Rajnikant, D inesK  M ousm i, Babu Varghese a n d  B andhan  Sharniathe non>hydrogcn atoms including their thermal parameters was carried out using SHELXI^93 software [8]. Final refinement with anisotropic thermal param eters o f  non-hydrogen atoms and fixing the hydrogen atom s stereochem ically  resulted  into R = 0.0598, wR2 = 0.1337. Atomic scattering factors were taken from International Tables for Crystallography (Tables 4.2.6.8 and 6.1.1.4, \b l. C, 1992). The crystallographic data for compound (I) are summarized in Table 1.Tiibic J. O y sta l data and structureCrystal descriptionEmpirical formulaFormula weightTemperatureRadiationW avelengthUnit cell dimensionsVolumeCrystal sy.siem  Space group Z, Calculated density F(OOO)No. o f reflections collectedReflections uniqueReflections ob.scrved [I >  2<y(I)j .R efinem ent methodData / restraints /  parametersG oodness-of-fit onFinal K  indices >  4<t F JR indices (all data)Largest diff. peak and holerefinement details.Rectangular plates C,,H,,N O,2 4 1 .2 8  2 9 3 (2 ) K M o K a  O 7 1 0 0 9  Aa ^ S .\ 15(3), b  = 19 .067(10) c == 8.383 (6 ) A, /? = 115 45(15)"1171 2(1!) A’M on oclin icP2 ,/n4 , 1.368 M g/m-5 1 22 2 8 52 0 5 81 0 9 0Full-matrix least-squares on2058 / 0  /1630 .9 5 0R1 = 0 .0598 , wR2 = 0  1337 R1 5= 0 .1149 , wR2 = 0.1548  0.26 < A p  < -  0.31 c A-'The final atomic coordinates and equivalent isotropic thermal parameters for non-hydrogen atoms are given in Table 2. The bond distances and bond angles are presented in Table 3. An ORTEP view o f the m olecule with the atomic numbering scheme is shown in Figure 2[9]. The geometrical calculations were performed by using the PARST program 110]-The bond distances and bond angles in the coumarin moeity are normal and are in good agreement with analogous structures [11-15]. The fused benzene ring A and pyrone ring B arc almost planar and dihedral angle between the two rings is 0.6{ 1 thus making the coumarin moiety close to planar. The piperidine ring C of the molecule adopts d is to r te d  so fa  conformation with asymmetry parameters [16] A C s { C l)  ^  8.89 and piperdine ring D  o f the molecule exists in d is to r te d  c h a ir  conformation withTable 2.(A^) for A tomo iC2C3C 4C5C6C lC8C9CIO01 IC l 2CM3C 14N I5CI6C 17C I 8Atom ic coordinates and equivalent isotropic thermal parameicts all the non-hydrogen atoms (e .s.d .’s in parentheses)Z IJ- *0 .1 6 3 3  (2 ) 0 ,4 0 1 5 (1 ) 0 3051 (2 ) 0 .0 4 8  ( 1)0 .1321  (4 ) 0 .3 3 6 6  (2 ) 0 .2251  (4) 0 .0 5 4  ( 1)-0 .0 3 7 6  (4 ) 0 .3 2 6 9  (2 ) 0 .0 7 1 9  (4) 0 .0 5 5  ( 1)- 0  1581 (4 ) 0 .3 7 9 4  ( 1) 0 .0 0 9 0  (3 ) 0 0 5 0  ( 1)- 0 .2 4 5 3  (3 ) 0 .5 0 3 8  ( 1) 0 .0 3 7 8  (3) 0 043  ( 1 )- 0  2 0 6 9  (3 ) 0 .5 6 6 6  ( I ) 0 .1 2 5 4  (3) 0 .0 4 2  ( 1 1-0 .0 -3 6 0  (3 ) 0  5 7 4 6  (1 ) 0 .2 7 8 9  (3) 0 038 (1 10 .0 8 6 9  (3 ) 0 .5 1 7 6  ( 1) 0 .3 3 6 8  (3) 0 039  ( I )0  0 3 9 4  (3) 0 .4 5 6 0  (1 ) 0 .2 4 2 8  (3) 0 0 4 0  ( 1 )-0 .1 2 6 1  (3 ) 0 4 4 6 2  (1 ) 0 .0 9 2 6  (3) 0 042 ( 1 )0  25 2 8  (3) 0 29 3 4  (1 ) 0 .2 9 0 7  (3 ) 0 077  ( 1 )- 0 .3 3 6 9  (3 ) 0 6 2 7 6  (1 ) 0 .0 6 9 3  (3) 0 054  ( 1 1-0 .3 2 0 5  (4 ) 0 .6 6 8 0  ( 2 ) 0  2327  (4 ) 0 .0 5 8  ( 1 )- 0  1265 (4 ) 0 .6 9 3 4  (2 ) 0 .3 2 9 8  (4) 0 0 62  ( 1}0 .0 0 5 5  (3) 0 .6 3 6 5  (1 ) 0 3697  (3) 0 0 49  ( I )0 I8 6 0  (4) 0 6 5 1 8  (2) 0  5071 (4) 0 063  ( 1)0 .3 2 8 9  (4) 0  6021 ( 2 ) 0 .5 1 2 5  (4) 0 064 ( 1 )0  2667  (3 ) 0 526 8  ( 1 > 0 .4 9 7 5  (3) 0 052 (1 )-  ( 1 /3 )2 ; ,2 //y ^ 7 ;a ;(r7 ,.« ,)0 4F ig u re  2. ORTEP v iew  o f  the m o lecu le , w ith d isp lacem ent ellipsouJ^ drawn at the 50% probability level.asymmetry parameters AC2(C7—C15) = 13.2 and AC.y(C7)12.2 .Tlie molecules o f (I) are linked by two intermolecular C-H. . .0  hydrogen bonds as given in Table 4. The symmetry related Ol 1 at (jr-1/2, —y + 1/2, +Z—1/2) and ( - jc, -y + l) , -z )  arc hydrogen bonded to C3 and C 12 at (x, y, z). Based on the compiled data for a large number o f C -H ...O  contacts, Steiner and Desiraju [171 find significant statistical directionality and the C-H.. 0  interactions in (/) may be termed as *wcak' hydrogen bond, with a greater contribution to packing forces than simple van der Waals interactions. A view o f the molecules down c-axis in theX-ray structural analysis o f  IH, 4H-terahydroquinolizino-(9,9a, !gh) coumarinAcknowledgment75Table 3. Bond d istances (A) and bond angles (") for all non-hydrogen  atoms (e.s.d.'s are given in parentheses).O) -  C2 01 -  C9 C2 -  0 1 1 CS -  C'9 fY) -  C7 C8 -  C I8I 378  (4 )  1.383 (3 )  1.215 (4 )  1 .374 (3 )  1.438 (3 )  1.512 (3 )N I5  -  C 14  N 15 -  C 16  N 15 -  C7 C I4  ~  C l 3 C17 -  C I6 C18 -- C171 459  (4) 1.452 (3 )  1.366 (4) 1 508 (4 )  1.483 <^ 5) 1 509unit cell show s th e ir  p lacem en t in rev ersed  o rien ta tio n  (Figure 3).Figure 3. Packing diagram, viewed down the r -axis.We are thankful to the Council o f  Scientific and Industrial Research, New D elhi, Govt, o f  India for funding under a sponsored research scheme.R e fe re n c e sinC13 -  C l 2 1.527 (4 ) C l 2 -  C6 1 503 12]C’I6 -  N I5 C l 122.6 ( 2 ) C18 -  C8 -  C7 1 19.0CI4 -  N15 -  C7 122.3 (2) C 8 -  C l8 -  C l7 1 10.2 ( 2 )C 2 -  OI -  C9 122.6 (2 ) C18 -  C17 -  C 16 1121  i2) 13]N!5 -  C14 -  C13 1 12.2 (2 ) N15 -  C 16 -  C I7 1 1 3 9  <2 )|4 ]C14 -  C13 ~  C12 108 3 (2) N 15 -  C7 -  C8 120-3 (1)( 1 3  -  C I2 -  C6 109.3 (2 ) N I5  -  C'7 -  C6 120 1 i2)15]C12 -  C6 -  C7 118.4  (2 )Table 4 . G eom etry o f  in tcrm olecular interaction (c s parentheses)d's are given in [6 ]D -H  A D A (A) H A (A) D -H  A C‘) 17]C3~H3. 3 .29  (4 ) 2 35 (4 ) 153 1 ( I )("12-H I2B . .O l 3 .6 9  (4 ) 2 76  (4 ) 161 5 (4) 18]Symmetry code ( i)  x -  1/2 . -  y 4 1/2, z -  1/2, ( I t)  -A . - -V I, -  z. 19]lio ji m[121113]114][15]116]117]I Wol.ska, T  Borow iak and M CJawrun A cta  C rvst. C 4 6  2 1 4 6  (1 9 9 0 )1 W einm ann H is to ry  o j  the D e v e lo p m e n t & A p p lira tio r is  o f  C'oumarin an d  C ou m arm -rela ted  C om pounds  (Chiche.stcr ; John W iley) p i (19 9 7 )K H Drexhage in Dye Lxisvrs. Topic tn A pplied  Physics Vol. 1 (cd) F P Schafci ch 4 (N ew  York . Springer-Verlag) (1973)S A Tuccio, K H Drexhage and G A Reynolds <}pt. Commun. 1 248 (1 9 7 3 )G A R ey n o ld s and K H D rexh age O pt. C om m un. 13 2 2 2  (1 9 7 5 )J B Marling. J G Hawley, E M Liston and W B Grant Appl. O pt 13 2317  (1 9 7 4 )G M Sheld rick , S H E L X S 86 . P ro g ra m  f o r  C r y s ta l  S tru c tu re  D eterm in a tion  (U n iversity  o f  G ottingen . Federal R epublic  o f  G erm any) (19 8 6 )G M Sheldrick, SH ELXL93 Program  f o r  Refinem ent o f  CTystal Structures (IJniversHy o f  Ciotlingen. G erm any) (19 9 3 )L J Farrugia J Appl Cry.st 30  565 (1997)M Nardelli J. A ppl Crxst 28  659  (1995)K Rajalakshmt. N Jain. S D eepthi, H G K nshnam urthy and V Pattabhi A ria  Cry.st C 55 813 (1999)K A Solomon. S S Rajan, G Gopaiakrishna, V Kashinath and V P Santhana A cta  Cry.st, C 59  (2002)A Usman, A Razak, H K Fun, S Chantrapromma, B~G Zhao and J-H Xu A cta Cry.st K58 57 (2(K)2)R Krishna, P G Arvindan, M Yogavel, Vclmurugan, S S S Raj, H K Fun. M S Sundaram and R Raghunathan, A cta  Cryst., E 59  1395 (2 0 0 3 )Rajntkant. D inesh. Kamni and Bandhan Sharma Indian J Pure  Appl. Phys. 42  524 (2004)W L Duax and D A Norton Atlas o f  S teroidal Strut'iure 1 (N ew  York ; Planum ) (1975)G J Desiraju and T Steiner The Weak Hydrogen Bond  (lUCY, New  Y o r k ) (1 9 9 9 )

X-Ray Structural Analysis of 1H, 4H-Terahydroquinolizino-(9,9A, Igh) Coumarin

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X-Ray Structural Analysis of 1H, 4H-Terahydroquinolizino-(9,9A, Igh) Coumarin

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