organic compounds
rac-5′′-(4-Fluorobenzylidene)-1′-(4-fluorophenyl)-1′′-methyl-1′,2′,3′,5′,6′,7′,8′,8a′-octahydrodispiro[acenaphthylene-1,3′-indolizine-2′,3′′-piperidine]-2,4′′(1H)-dione
aDepartment of Physics, The Madura College, Madurai 625 011, India, bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and cDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
*Correspondence e-mail: plakshmannilantha@ymail.com
In the title E isomer of the C37H32F2N2O2, the pyridinone ring adopts a twisted half-chair conformation with the N atom deviating by −0.355 (3) Å and with the methylene C atom next to octahydroindolizine moiety deviating by 0.415 (3) Å from the mean plane defined by other four atoms. In the octahydroindolizine system, the pyrrolidine ring exhibits an with the fused methyne C atom deviating by 0.6496 (1) Å from the mean plane defined by four other atoms, and the piperidine ring exhibits a distorted chair conformation as evident from the puckering parameters Q = 0.568 (2) Å, θ = 1.0 (2) and Φ = 256 (11)°. In the crystal, C—H⋯O interactions connect the molecules into chains along [101].
Related literature
For general properties of indolizines, see: Malonne et al. (1998); Medda et al. (2003); Pearson & Guo (2001). For related structures, see: Sussman & Wodak (1973); Wodak (1975). For ring conformation analysis, see: Cremer & Pople (1975).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812051094/ld2088sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812051094/ld2088Isup2.hkl
A mixture of 1-methyl-3,5-bis[(E)-4-fluromethylidene]tetrahydro-4(1H)- pyridinone (1 mmol), acenaphthenequinone (1 mmol) and piperidine-2- carboxylic acid (1 mmol) was dissolved in isopropyl alcohol (15 ml) and heated to reflux for 60 min. After completion of the reaction, as evident from TLC, the mixture was poured into water (50 ml), the precipitated solid was filtered and washed with water (100 ml) to obtain pure yellow solid. Melting point:498 K, Yield: 93%
H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.98 Å; Uiso = 1.2Ueq(C) for CH2 and CH groups, and Uiso = 1.5Ueq(C) for CH3 groups. The (0 1 1) reflection was probably affected by the beam-stop and was omitted from the refinement.
Indolizine derivatives have been found to possess a variety of biological activities such as anti-inflammatory (Malonne et al., 1998), antiviral (Medda et al., 2003) and anti-tumor (Pearson & Guo, 2001) activities. In view of its medicinal importance and in conjunction with our research interests, we synthesized the title compound and report here its X-ray structure.
In the title compound (Fig.1), the pyridinone ring adopts twisted half chair conformation with atoms N2 and C2 deviating by -0.355 (3)Å and 0.415 (3)Å respectively, from the mean plane defined by other atoms C3/C4/C5/C6. The sum of bond angles around N2 (332.65 (1) °) indicates a pyramidal geometry. Although the atoms C1, C2, C6 attached to the atom N2, are all in Sp2 θ = 1.0 (2)° and Φ = 256 (11)° (Cremer & Pople, 1975). The twist of the 4-fluorobenzene ring (C52-C57) with respect to the spiro junction is denoted by the torsion angle C5-C51-C52-C57 (-49.1 (2) °). The dihedral angle between the mean plane of the pyridinone ring, defined by the atoms C2/C4/C5/C6 with the two 4-fluorobenzene rings are 87.70 (1) ° and 63.20 (1)°. The carbonyl bond length, i.e C4=O1 (1.214 (2) Å), is somewhat longer, due to C—H···O contacts. The C8—N1 bond length (1.456 (2) Å) is comparable with the CSp2—NSp2 distance found in similar structures (Sussman & Wodak, 1973; Wodak, 1975).
their different environments cause differences in bond lengths (N2-C2 (1.4467 (19) Å) and N2-C6 (1.457 (2) Å)) and in the bond angles (C1-N2-C2 (112.35 (13) °), C1-N2-C6 (111.00 (14) °) and C2-N2-C6 (109.31 (12) °)). The methyl group at position 1 of the pyridinone ring is in equatorial orientation, denoted by the torsion angle C1-N2-C6-C5 (177.38 (1) °). In the fused system , the pyrrolidine ring adopts the twisted with C8 atom at the flap deviating by 0.6496 (1) Å from the mean plane defined by other atoms C7/C3/C13/N1 and this orientation may be due to the intra-molecular C7—H7···O1 interaction. In the fused system the piperidine ring adopts a slightly distorted chair conformation as evident from the puckering parameters Q = 0.568 (2) Å,The structure is stabilized by intermolecular C11—H11A···O1 interactions generating chains along [101] (Fig. 2).
For general properties of indolizines, see: Malonne et al. (1998); Medda et al. (2003); Pearson & Guo (2001). For related structures, see: Sussman & Wodak (1973); Wodak (1975). For ring conformation analysis, see: Cremer & Pople (1975).
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of (I), showing 20% probability displacement ellipsoids and the atom-numbering scheme. | |
Fig. 2. Partial packing diagram showing C—H···O interactions. |
C37H32F2N2O2 | F(000) = 1208 |
Mr = 574.65 | Dx = 1.300 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2000 reflections |
a = 10.2716 (4) Å | θ = 2–31° |
b = 20.0353 (7) Å | µ = 0.09 mm−1 |
c = 14.3790 (6) Å | T = 293 K |
β = 97.047 (1)° | Block, yellow |
V = 2936.8 (2) Å3 | 0.21 × 0.19 × 0.18 mm |
Z = 4 |
Bruker Kappa APEXII diffractometer | 7519 independent reflections |
Radiation source: fine-focus sealed tube | 4823 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 0 pixels mm-1 | θmax = 28.6°, θmin = 2.0° |
ω and φ scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −27→27 |
Tmin = 0.967, Tmax = 0.974 | l = −19→19 |
33177 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.8383P] where P = (Fo2 + 2Fc2)/3 |
7519 reflections | (Δ/σ)max < 0.001 |
388 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C37H32F2N2O2 | V = 2936.8 (2) Å3 |
Mr = 574.65 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.2716 (4) Å | µ = 0.09 mm−1 |
b = 20.0353 (7) Å | T = 293 K |
c = 14.3790 (6) Å | 0.21 × 0.19 × 0.18 mm |
β = 97.047 (1)° |
Bruker Kappa APEXII diffractometer | 7519 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4823 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.974 | Rint = 0.033 |
33177 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.22 e Å−3 |
7519 reflections | Δρmin = −0.21 e Å−3 |
388 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R -factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of (F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R -factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.61115 (10) | 0.19654 (5) | 0.39944 (8) | 0.0470 (3) | |
N1 | 0.39601 (12) | 0.29516 (7) | 0.21792 (9) | 0.0406 (3) | |
N2 | 0.30062 (12) | 0.28413 (6) | 0.49902 (9) | 0.0409 (3) | |
C3 | 0.45465 (13) | 0.28569 (7) | 0.38350 (10) | 0.0333 (3) | |
C2 | 0.39870 (15) | 0.32425 (7) | 0.46112 (11) | 0.0378 (3) | |
H2A | 0.4686 | 0.3352 | 0.5104 | 0.045* | |
H2B | 0.3596 | 0.3656 | 0.4362 | 0.045* | |
O2 | 0.18118 (12) | 0.35533 (6) | 0.31669 (9) | 0.0557 (3) | |
C5 | 0.44596 (14) | 0.18822 (7) | 0.49900 (11) | 0.0375 (3) | |
C4 | 0.51377 (14) | 0.22096 (7) | 0.42563 (10) | 0.0355 (3) | |
F1 | 0.30715 (12) | −0.05223 (6) | 0.77515 (9) | 0.0769 (4) | |
C13 | 0.34404 (13) | 0.26706 (7) | 0.29939 (10) | 0.0358 (3) | |
C7 | 0.55514 (14) | 0.32673 (7) | 0.33483 (11) | 0.0363 (3) | |
H7 | 0.6170 | 0.2946 | 0.3136 | 0.044* | |
C14 | 0.20618 (15) | 0.29644 (8) | 0.31472 (11) | 0.0410 (4) | |
C71 | 0.63601 (15) | 0.37673 (7) | 0.39573 (11) | 0.0390 (3) | |
C20 | 0.17940 (15) | 0.18241 (8) | 0.29535 (11) | 0.0434 (4) | |
C51 | 0.45644 (15) | 0.12233 (8) | 0.50714 (12) | 0.0433 (4) | |
H51 | 0.5001 | 0.1009 | 0.4627 | 0.052* | |
C52 | 0.40751 (15) | 0.07919 (7) | 0.57780 (12) | 0.0414 (4) | |
C21 | 0.31177 (14) | 0.19344 (8) | 0.28438 (11) | 0.0391 (3) | |
C8 | 0.47433 (15) | 0.35371 (8) | 0.24735 (11) | 0.0420 (4) | |
H8 | 0.4176 | 0.3901 | 0.2638 | 0.050* | |
C6 | 0.36509 (17) | 0.23063 (8) | 0.55591 (12) | 0.0479 (4) | |
H6A | 0.2995 | 0.2032 | 0.5805 | 0.057* | |
H6B | 0.4210 | 0.2496 | 0.6085 | 0.057* | |
C56 | 0.39704 (17) | 0.05049 (9) | 0.73925 (13) | 0.0514 (4) | |
H56 | 0.4141 | 0.0606 | 0.8027 | 0.062* | |
C57 | 0.43161 (16) | 0.09393 (8) | 0.67207 (12) | 0.0478 (4) | |
H57 | 0.4721 | 0.1341 | 0.6907 | 0.057* | |
C15 | 0.11258 (15) | 0.24044 (9) | 0.31307 (11) | 0.0449 (4) | |
C22 | 0.38379 (17) | 0.14106 (9) | 0.25929 (13) | 0.0509 (4) | |
H22 | 0.4703 | 0.1472 | 0.2482 | 0.061* | |
C72 | 0.60036 (19) | 0.44278 (9) | 0.40225 (14) | 0.0574 (5) | |
H72 | 0.5223 | 0.4576 | 0.3690 | 0.069* | |
C1 | 0.21719 (19) | 0.32362 (9) | 0.55275 (15) | 0.0599 (5) | |
H1A | 0.1537 | 0.2951 | 0.5764 | 0.090* | |
H1B | 0.1727 | 0.3572 | 0.5131 | 0.090* | |
H1C | 0.2701 | 0.3447 | 0.6042 | 0.090* | |
C54 | 0.30853 (19) | −0.02399 (9) | 0.61792 (15) | 0.0588 (5) | |
H54 | 0.2654 | −0.0636 | 0.6002 | 0.071* | |
C76 | 0.75231 (16) | 0.35654 (9) | 0.44646 (12) | 0.0490 (4) | |
H76 | 0.7783 | 0.3122 | 0.4436 | 0.059* | |
C16 | −0.01960 (17) | 0.23783 (11) | 0.32096 (13) | 0.0597 (5) | |
H16 | −0.0663 | 0.2761 | 0.3323 | 0.072* | |
C53 | 0.34488 (18) | 0.01952 (8) | 0.55166 (13) | 0.0538 (4) | |
H53 | 0.3272 | 0.0088 | 0.4885 | 0.065* | |
C55 | 0.33711 (16) | −0.00765 (8) | 0.70981 (14) | 0.0497 (4) | |
F2 | 0.86998 (16) | 0.50943 (7) | 0.55739 (10) | 0.1067 (5) | |
C12 | 0.30442 (17) | 0.30500 (10) | 0.13328 (12) | 0.0555 (5) | |
H12A | 0.2417 | 0.3395 | 0.1438 | 0.067* | |
H12B | 0.2565 | 0.2640 | 0.1173 | 0.067* | |
C19 | 0.11871 (18) | 0.11956 (10) | 0.28474 (13) | 0.0575 (5) | |
C9 | 0.55224 (19) | 0.37571 (11) | 0.16992 (13) | 0.0612 (5) | |
H9A | 0.6165 | 0.3418 | 0.1601 | 0.073* | |
H9B | 0.5988 | 0.4167 | 0.1882 | 0.073* | |
C75 | 0.83110 (19) | 0.40116 (12) | 0.50153 (14) | 0.0656 (5) | |
H75 | 0.9091 | 0.3871 | 0.5356 | 0.079* | |
C23 | 0.3254 (2) | 0.07716 (9) | 0.25032 (15) | 0.0655 (5) | |
H23 | 0.3760 | 0.0412 | 0.2352 | 0.079* | |
C17 | −0.08141 (19) | 0.17526 (13) | 0.31121 (15) | 0.0726 (7) | |
H17 | −0.1706 | 0.1726 | 0.3166 | 0.087* | |
C73 | 0.6783 (2) | 0.48739 (10) | 0.45719 (16) | 0.0703 (6) | |
H73 | 0.6530 | 0.5317 | 0.4614 | 0.084* | |
C18 | −0.0162 (2) | 0.11856 (13) | 0.29418 (15) | 0.0728 (6) | |
H18 | −0.0613 | 0.0783 | 0.2886 | 0.087* | |
C74 | 0.7921 (2) | 0.46553 (11) | 0.50471 (14) | 0.0673 (6) | |
C11 | 0.3801 (2) | 0.32515 (12) | 0.05371 (13) | 0.0710 (6) | |
H11A | 0.3192 | 0.3339 | −0.0020 | 0.085* | |
H11B | 0.4370 | 0.2888 | 0.0399 | 0.085* | |
C10 | 0.4618 (2) | 0.38711 (13) | 0.07917 (14) | 0.0785 (7) | |
H10A | 0.4044 | 0.4247 | 0.0867 | 0.094* | |
H10B | 0.5137 | 0.3976 | 0.0291 | 0.094* | |
C24 | 0.1984 (2) | 0.06633 (10) | 0.26295 (15) | 0.0704 (6) | |
H24 | 0.1640 | 0.0234 | 0.2571 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0377 (6) | 0.0464 (6) | 0.0572 (7) | 0.0083 (5) | 0.0073 (5) | 0.0054 (5) |
N1 | 0.0363 (6) | 0.0506 (8) | 0.0334 (7) | −0.0070 (6) | −0.0015 (5) | 0.0022 (6) |
N2 | 0.0427 (7) | 0.0342 (7) | 0.0471 (8) | 0.0041 (5) | 0.0112 (6) | −0.0001 (6) |
C3 | 0.0329 (7) | 0.0312 (7) | 0.0348 (8) | 0.0000 (6) | 0.0001 (6) | 0.0000 (6) |
C2 | 0.0423 (8) | 0.0318 (7) | 0.0385 (8) | 0.0003 (6) | 0.0015 (7) | −0.0012 (6) |
O2 | 0.0534 (7) | 0.0513 (7) | 0.0606 (8) | 0.0169 (6) | −0.0003 (6) | 0.0027 (6) |
C5 | 0.0378 (7) | 0.0356 (8) | 0.0382 (8) | 0.0005 (6) | 0.0006 (6) | 0.0017 (6) |
C4 | 0.0334 (7) | 0.0343 (8) | 0.0368 (8) | −0.0007 (6) | −0.0030 (6) | −0.0036 (6) |
F1 | 0.0915 (8) | 0.0641 (7) | 0.0801 (8) | −0.0139 (6) | 0.0300 (7) | 0.0206 (6) |
C13 | 0.0309 (7) | 0.0386 (8) | 0.0369 (8) | 0.0005 (6) | 0.0002 (6) | 0.0003 (6) |
C7 | 0.0338 (7) | 0.0359 (8) | 0.0382 (8) | −0.0021 (6) | 0.0009 (6) | 0.0002 (6) |
C14 | 0.0370 (8) | 0.0490 (9) | 0.0355 (8) | 0.0059 (7) | −0.0008 (6) | 0.0013 (7) |
C71 | 0.0398 (8) | 0.0383 (8) | 0.0388 (8) | −0.0073 (6) | 0.0040 (7) | 0.0013 (6) |
C20 | 0.0413 (8) | 0.0525 (10) | 0.0352 (8) | −0.0091 (7) | −0.0003 (7) | −0.0011 (7) |
C51 | 0.0459 (8) | 0.0370 (8) | 0.0471 (9) | 0.0026 (7) | 0.0060 (7) | 0.0010 (7) |
C52 | 0.0417 (8) | 0.0314 (8) | 0.0511 (10) | 0.0020 (6) | 0.0054 (7) | 0.0009 (7) |
C21 | 0.0374 (7) | 0.0420 (8) | 0.0362 (8) | −0.0025 (6) | −0.0020 (6) | −0.0035 (6) |
C8 | 0.0411 (8) | 0.0435 (9) | 0.0397 (9) | −0.0050 (7) | −0.0011 (7) | 0.0045 (7) |
C6 | 0.0583 (10) | 0.0403 (9) | 0.0472 (10) | 0.0054 (7) | 0.0150 (8) | 0.0049 (7) |
C56 | 0.0553 (10) | 0.0495 (10) | 0.0482 (10) | −0.0011 (8) | 0.0018 (8) | 0.0038 (8) |
C57 | 0.0501 (9) | 0.0380 (8) | 0.0528 (10) | −0.0064 (7) | −0.0043 (8) | 0.0026 (7) |
C15 | 0.0342 (8) | 0.0641 (11) | 0.0356 (8) | −0.0031 (7) | 0.0016 (6) | 0.0011 (7) |
C22 | 0.0479 (9) | 0.0498 (10) | 0.0531 (10) | 0.0015 (8) | −0.0012 (8) | −0.0127 (8) |
C72 | 0.0640 (11) | 0.0411 (10) | 0.0646 (12) | −0.0049 (8) | −0.0023 (9) | 0.0009 (8) |
C1 | 0.0653 (11) | 0.0504 (11) | 0.0696 (13) | 0.0120 (9) | 0.0300 (10) | 0.0006 (9) |
C54 | 0.0687 (12) | 0.0400 (9) | 0.0706 (13) | −0.0163 (8) | 0.0208 (10) | −0.0075 (9) |
C76 | 0.0442 (9) | 0.0558 (10) | 0.0453 (10) | −0.0037 (7) | −0.0009 (7) | −0.0030 (8) |
C16 | 0.0393 (9) | 0.0945 (15) | 0.0459 (10) | −0.0019 (9) | 0.0078 (8) | 0.0022 (10) |
C53 | 0.0679 (11) | 0.0416 (9) | 0.0529 (11) | −0.0070 (8) | 0.0113 (9) | −0.0083 (8) |
C55 | 0.0465 (9) | 0.0421 (9) | 0.0631 (12) | 0.0001 (7) | 0.0164 (8) | 0.0098 (8) |
F2 | 0.1306 (12) | 0.1010 (11) | 0.0827 (10) | −0.0629 (9) | −0.0102 (9) | −0.0266 (8) |
C12 | 0.0488 (9) | 0.0757 (13) | 0.0387 (9) | −0.0100 (9) | −0.0075 (8) | 0.0055 (9) |
C19 | 0.0574 (11) | 0.0648 (12) | 0.0486 (10) | −0.0234 (9) | −0.0004 (9) | −0.0006 (9) |
C9 | 0.0575 (11) | 0.0785 (13) | 0.0465 (10) | −0.0232 (10) | 0.0018 (8) | 0.0115 (9) |
C75 | 0.0523 (11) | 0.0899 (16) | 0.0509 (11) | −0.0152 (10) | −0.0089 (9) | −0.0055 (10) |
C23 | 0.0784 (14) | 0.0469 (11) | 0.0673 (13) | 0.0027 (10) | −0.0068 (11) | −0.0180 (9) |
C17 | 0.0425 (10) | 0.119 (2) | 0.0568 (13) | −0.0283 (12) | 0.0080 (9) | 0.0046 (12) |
C73 | 0.0943 (16) | 0.0439 (11) | 0.0718 (14) | −0.0180 (10) | 0.0065 (12) | −0.0088 (10) |
C18 | 0.0616 (12) | 0.0925 (17) | 0.0635 (13) | −0.0370 (12) | 0.0041 (10) | −0.0013 (12) |
C74 | 0.0825 (14) | 0.0662 (13) | 0.0521 (12) | −0.0346 (11) | 0.0039 (11) | −0.0132 (10) |
C11 | 0.0660 (12) | 0.1065 (18) | 0.0376 (10) | −0.0204 (12) | −0.0053 (9) | 0.0102 (10) |
C10 | 0.0806 (14) | 0.1072 (18) | 0.0451 (11) | −0.0291 (13) | −0.0032 (10) | 0.0243 (11) |
C24 | 0.0858 (15) | 0.0498 (11) | 0.0715 (14) | −0.0212 (11) | −0.0065 (12) | −0.0115 (10) |
O1—C4 | 1.2142 (17) | C57—H57 | 0.9300 |
N1—C8 | 1.456 (2) | C15—C16 | 1.377 (2) |
N1—C12 | 1.457 (2) | C22—C23 | 1.413 (3) |
N1—C13 | 1.4588 (19) | C22—H22 | 0.9300 |
N2—C2 | 1.4467 (19) | C72—C73 | 1.382 (3) |
N2—C1 | 1.456 (2) | C72—H72 | 0.9300 |
N2—C6 | 1.457 (2) | C1—H1A | 0.9600 |
C3—C4 | 1.5255 (19) | C1—H1B | 0.9600 |
C3—C2 | 1.526 (2) | C1—H1C | 0.9600 |
C3—C7 | 1.552 (2) | C54—C55 | 1.358 (3) |
C3—C13 | 1.5987 (19) | C54—C53 | 1.376 (3) |
C2—H2A | 0.9700 | C54—H54 | 0.9300 |
C2—H2B | 0.9700 | C76—C75 | 1.387 (2) |
O2—C14 | 1.2084 (19) | C76—H76 | 0.9300 |
C5—C51 | 1.329 (2) | C16—C17 | 1.404 (3) |
C5—C4 | 1.486 (2) | C16—H16 | 0.9300 |
C5—C6 | 1.499 (2) | C53—H53 | 0.9300 |
F1—C55 | 1.3587 (19) | F2—C74 | 1.356 (2) |
C13—C21 | 1.521 (2) | C12—C11 | 1.515 (3) |
C13—C14 | 1.574 (2) | C12—H12A | 0.9700 |
C7—C71 | 1.511 (2) | C12—H12B | 0.9700 |
C7—C8 | 1.519 (2) | C19—C24 | 1.403 (3) |
C7—H7 | 0.9800 | C19—C18 | 1.409 (3) |
C14—C15 | 1.476 (2) | C9—C10 | 1.523 (3) |
C71—C72 | 1.379 (2) | C9—H9A | 0.9700 |
C71—C76 | 1.382 (2) | C9—H9B | 0.9700 |
C20—C15 | 1.390 (2) | C75—C74 | 1.353 (3) |
C20—C19 | 1.405 (2) | C75—H75 | 0.9300 |
C20—C21 | 1.405 (2) | C23—C24 | 1.356 (3) |
C51—C52 | 1.469 (2) | C23—H23 | 0.9300 |
C51—H51 | 0.9300 | C17—C18 | 1.356 (3) |
C52—C57 | 1.380 (2) | C17—H17 | 0.9300 |
C52—C53 | 1.387 (2) | C73—C74 | 1.352 (3) |
C21—C22 | 1.358 (2) | C73—H73 | 0.9300 |
C8—C9 | 1.514 (2) | C18—H18 | 0.9300 |
C8—H8 | 0.9800 | C11—C10 | 1.518 (3) |
C6—H6A | 0.9700 | C11—H11A | 0.9700 |
C6—H6B | 0.9700 | C11—H11B | 0.9700 |
C56—C55 | 1.361 (2) | C10—H10A | 0.9700 |
C56—C57 | 1.379 (2) | C10—H10B | 0.9700 |
C56—H56 | 0.9300 | C24—H24 | 0.9300 |
C8—N1—C12 | 114.26 (13) | C21—C22—C23 | 119.06 (17) |
C8—N1—C13 | 108.73 (12) | C21—C22—H22 | 120.5 |
C12—N1—C13 | 117.42 (12) | C23—C22—H22 | 120.5 |
C2—N2—C1 | 112.35 (13) | C71—C72—C73 | 121.29 (18) |
C2—N2—C6 | 109.31 (12) | C71—C72—H72 | 119.4 |
C1—N2—C6 | 111.00 (14) | C73—C72—H72 | 119.4 |
C4—C3—C2 | 107.90 (12) | N2—C1—H1A | 109.5 |
C4—C3—C7 | 112.03 (11) | N2—C1—H1B | 109.5 |
C2—C3—C7 | 113.10 (12) | H1A—C1—H1B | 109.5 |
C4—C3—C13 | 108.25 (11) | N2—C1—H1C | 109.5 |
C2—C3—C13 | 112.02 (11) | H1A—C1—H1C | 109.5 |
C7—C3—C13 | 103.47 (11) | H1B—C1—H1C | 109.5 |
N2—C2—C3 | 109.64 (12) | C55—C54—C53 | 118.44 (16) |
N2—C2—H2A | 109.7 | C55—C54—H54 | 120.8 |
C3—C2—H2A | 109.7 | C53—C54—H54 | 120.8 |
N2—C2—H2B | 109.7 | C71—C76—C75 | 121.25 (18) |
C3—C2—H2B | 109.7 | C71—C76—H76 | 119.4 |
H2A—C2—H2B | 108.2 | C75—C76—H76 | 119.4 |
C51—C5—C4 | 117.46 (14) | C15—C16—C17 | 117.6 (2) |
C51—C5—C6 | 124.01 (15) | C15—C16—H16 | 121.2 |
C4—C5—C6 | 118.47 (13) | C17—C16—H16 | 121.2 |
O1—C4—C5 | 121.20 (13) | C54—C53—C52 | 120.95 (18) |
O1—C4—C3 | 121.49 (14) | C54—C53—H53 | 119.5 |
C5—C4—C3 | 117.30 (12) | C52—C53—H53 | 119.5 |
N1—C13—C21 | 110.80 (12) | C54—C55—F1 | 118.30 (16) |
N1—C13—C14 | 113.10 (12) | C54—C55—C56 | 123.00 (17) |
C21—C13—C14 | 101.45 (12) | F1—C55—C56 | 118.68 (17) |
N1—C13—C3 | 102.78 (11) | N1—C12—C11 | 109.17 (14) |
C21—C13—C3 | 117.13 (12) | N1—C12—H12A | 109.8 |
C14—C13—C3 | 112.01 (12) | C11—C12—H12A | 109.8 |
C71—C7—C8 | 116.73 (12) | N1—C12—H12B | 109.8 |
C71—C7—C3 | 116.03 (12) | C11—C12—H12B | 109.8 |
C8—C7—C3 | 103.64 (11) | H12A—C12—H12B | 108.3 |
C71—C7—H7 | 106.6 | C24—C19—C20 | 116.23 (17) |
C8—C7—H7 | 106.6 | C24—C19—C18 | 128.21 (19) |
C3—C7—H7 | 106.6 | C20—C19—C18 | 115.51 (19) |
O2—C14—C15 | 127.07 (15) | C8—C9—C10 | 110.59 (15) |
O2—C14—C13 | 124.46 (14) | C8—C9—H9A | 109.5 |
C15—C14—C13 | 107.99 (13) | C10—C9—H9A | 109.5 |
C72—C71—C76 | 117.69 (15) | C8—C9—H9B | 109.5 |
C72—C71—C7 | 122.95 (14) | C10—C9—H9B | 109.5 |
C76—C71—C7 | 119.35 (14) | H9A—C9—H9B | 108.1 |
C15—C20—C19 | 123.18 (16) | C74—C75—C76 | 118.64 (19) |
C15—C20—C21 | 113.29 (14) | C74—C75—H75 | 120.7 |
C19—C20—C21 | 123.46 (16) | C76—C75—H75 | 120.7 |
C5—C51—C52 | 127.93 (15) | C24—C23—C22 | 122.47 (19) |
C5—C51—H51 | 116.0 | C24—C23—H23 | 118.8 |
C52—C51—H51 | 116.0 | C22—C23—H23 | 118.8 |
C57—C52—C53 | 118.16 (16) | C18—C17—C16 | 122.57 (18) |
C57—C52—C51 | 121.22 (14) | C18—C17—H17 | 118.7 |
C53—C52—C51 | 120.41 (16) | C16—C17—H17 | 118.7 |
C22—C21—C20 | 118.31 (15) | C74—C73—C72 | 118.93 (19) |
C22—C21—C13 | 132.12 (14) | C74—C73—H73 | 120.5 |
C20—C21—C13 | 109.48 (13) | C72—C73—H73 | 120.5 |
N1—C8—C9 | 110.11 (14) | C17—C18—C19 | 121.27 (19) |
N1—C8—C7 | 100.39 (12) | C17—C18—H18 | 119.4 |
C9—C8—C7 | 115.35 (13) | C19—C18—H18 | 119.4 |
N1—C8—H8 | 110.2 | C73—C74—C75 | 122.20 (18) |
C9—C8—H8 | 110.2 | C73—C74—F2 | 119.1 (2) |
C7—C8—H8 | 110.2 | C75—C74—F2 | 118.7 (2) |
N2—C6—C5 | 110.76 (13) | C12—C11—C10 | 110.83 (18) |
N2—C6—H6A | 109.5 | C12—C11—H11A | 109.5 |
C5—C6—H6A | 109.5 | C10—C11—H11A | 109.5 |
N2—C6—H6B | 109.5 | C12—C11—H11B | 109.5 |
C5—C6—H6B | 109.5 | C10—C11—H11B | 109.5 |
H6A—C6—H6B | 108.1 | H11A—C11—H11B | 108.1 |
C55—C56—C57 | 117.91 (17) | C11—C10—C9 | 110.19 (17) |
C55—C56—H56 | 121.0 | C11—C10—H10A | 109.6 |
C57—C56—H56 | 121.0 | C9—C10—H10A | 109.6 |
C56—C57—C52 | 121.51 (16) | C11—C10—H10B | 109.6 |
C56—C57—H57 | 119.2 | C9—C10—H10B | 109.6 |
C52—C57—H57 | 119.2 | H10A—C10—H10B | 108.1 |
C16—C15—C20 | 119.84 (17) | C23—C24—C19 | 120.37 (18) |
C16—C15—C14 | 132.40 (17) | C23—C24—H24 | 119.8 |
C20—C15—C14 | 107.67 (13) | C19—C24—H24 | 119.8 |
C1—N2—C2—C3 | −163.25 (14) | C12—N1—C8—C7 | 179.61 (13) |
C6—N2—C2—C3 | 73.06 (15) | C13—N1—C8—C7 | 46.28 (15) |
C4—C3—C2—N2 | −58.85 (14) | C71—C7—C8—N1 | −170.67 (13) |
C7—C3—C2—N2 | 176.66 (11) | C3—C7—C8—N1 | −41.77 (14) |
C13—C3—C2—N2 | 60.20 (15) | C71—C7—C8—C9 | 71.06 (19) |
C51—C5—C4—O1 | −27.6 (2) | C3—C7—C8—C9 | −160.05 (14) |
C6—C5—C4—O1 | 155.33 (15) | C2—N2—C6—C5 | −58.13 (17) |
C51—C5—C4—C3 | 151.39 (14) | C1—N2—C6—C5 | 177.38 (14) |
C6—C5—C4—C3 | −25.72 (19) | C51—C5—C6—N2 | −141.71 (16) |
C2—C3—C4—O1 | −145.48 (14) | C4—C5—C6—N2 | 35.2 (2) |
C7—C3—C4—O1 | −20.35 (19) | C55—C56—C57—C52 | −0.5 (3) |
C13—C3—C4—O1 | 93.10 (15) | C53—C52—C57—C56 | 1.1 (3) |
C2—C3—C4—C5 | 35.57 (16) | C51—C52—C57—C56 | −173.68 (15) |
C7—C3—C4—C5 | 160.70 (12) | C19—C20—C15—C16 | 0.0 (3) |
C13—C3—C4—C5 | −85.85 (15) | C21—C20—C15—C16 | 176.90 (15) |
C8—N1—C13—C21 | −156.45 (12) | C19—C20—C15—C14 | −177.03 (15) |
C12—N1—C13—C21 | 71.89 (17) | C21—C20—C15—C14 | −0.10 (19) |
C8—N1—C13—C14 | 90.42 (14) | O2—C14—C15—C16 | −6.2 (3) |
C12—N1—C13—C14 | −41.24 (19) | C13—C14—C15—C16 | −178.49 (17) |
C8—N1—C13—C3 | −30.55 (14) | O2—C14—C15—C20 | 170.25 (16) |
C12—N1—C13—C3 | −162.21 (14) | C13—C14—C15—C20 | −2.01 (17) |
C4—C3—C13—N1 | −116.32 (13) | C20—C21—C22—C23 | −3.5 (3) |
C2—C3—C13—N1 | 124.84 (12) | C13—C21—C22—C23 | −179.66 (17) |
C7—C3—C13—N1 | 2.70 (14) | C76—C71—C72—C73 | 0.3 (3) |
C4—C3—C13—C21 | 5.37 (17) | C7—C71—C72—C73 | −178.59 (17) |
C2—C3—C13—C21 | −113.47 (14) | C72—C71—C76—C75 | −0.5 (3) |
C7—C3—C13—C21 | 124.39 (13) | C7—C71—C76—C75 | 178.47 (16) |
C4—C3—C13—C14 | 121.97 (13) | C20—C15—C16—C17 | 0.5 (3) |
C2—C3—C13—C14 | 3.13 (17) | C14—C15—C16—C17 | 176.62 (17) |
C7—C3—C13—C14 | −119.01 (13) | C55—C54—C53—C52 | −1.0 (3) |
C4—C3—C7—C71 | −90.36 (15) | C57—C52—C53—C54 | −0.4 (3) |
C2—C3—C7—C71 | 31.85 (17) | C51—C52—C53—C54 | 174.44 (16) |
C13—C3—C7—C71 | 153.26 (12) | C53—C54—C55—F1 | −176.69 (16) |
C4—C3—C7—C8 | 140.32 (12) | C53—C54—C55—C56 | 1.7 (3) |
C2—C3—C7—C8 | −97.48 (14) | C57—C56—C55—C54 | −1.0 (3) |
C13—C3—C7—C8 | 23.94 (14) | C57—C56—C55—F1 | 177.38 (15) |
N1—C13—C14—O2 | −50.7 (2) | C8—N1—C12—C11 | 58.8 (2) |
C21—C13—C14—O2 | −169.40 (15) | C13—N1—C12—C11 | −172.14 (16) |
C3—C13—C14—O2 | 64.89 (19) | C15—C20—C19—C24 | 177.26 (17) |
N1—C13—C14—C15 | 121.82 (14) | C21—C20—C19—C24 | 0.6 (3) |
C21—C13—C14—C15 | 3.12 (15) | C15—C20—C19—C18 | −0.6 (3) |
C3—C13—C14—C15 | −122.59 (13) | C21—C20—C19—C18 | −177.23 (17) |
C8—C7—C71—C72 | 29.5 (2) | N1—C8—C9—C10 | 54.8 (2) |
C3—C7—C71—C72 | −93.20 (19) | C7—C8—C9—C10 | 167.53 (17) |
C8—C7—C71—C76 | −149.41 (15) | C71—C76—C75—C74 | −0.1 (3) |
C3—C7—C71—C76 | 87.91 (17) | C21—C22—C23—C24 | 2.1 (3) |
C4—C5—C51—C52 | 175.06 (15) | C15—C16—C17—C18 | −0.3 (3) |
C6—C5—C51—C52 | −8.0 (3) | C71—C72—C73—C74 | 0.5 (3) |
C5—C51—C52—C57 | −49.1 (2) | C16—C17—C18—C19 | −0.4 (3) |
C5—C51—C52—C53 | 136.24 (18) | C24—C19—C18—C17 | −176.8 (2) |
C15—C20—C21—C22 | −174.76 (15) | C20—C19—C18—C17 | 0.8 (3) |
C19—C20—C21—C22 | 2.2 (2) | C72—C73—C74—C75 | −1.1 (3) |
C15—C20—C21—C13 | 2.26 (19) | C72—C73—C74—F2 | 178.86 (19) |
C19—C20—C21—C13 | 179.18 (15) | C76—C75—C74—C73 | 1.0 (3) |
N1—C13—C21—C22 | 52.9 (2) | C76—C75—C74—F2 | −179.02 (17) |
C14—C13—C21—C22 | 173.26 (17) | N1—C12—C11—C10 | −56.4 (2) |
C3—C13—C21—C22 | −64.5 (2) | C12—C11—C10—C9 | 55.7 (3) |
N1—C13—C21—C20 | −123.54 (13) | C8—C9—C10—C11 | −54.6 (3) |
C14—C13—C21—C20 | −3.20 (16) | C22—C23—C24—C19 | 0.8 (3) |
C3—C13—C21—C20 | 119.04 (14) | C20—C19—C24—C23 | −2.1 (3) |
C12—N1—C8—C9 | −58.33 (18) | C18—C19—C24—C23 | 175.5 (2) |
C13—N1—C8—C9 | 168.34 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···O1i | 0.97 | 2.49 | 3.352 (2) | 148 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C37H32F2N2O2 |
Mr | 574.65 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.2716 (4), 20.0353 (7), 14.3790 (6) |
β (°) | 97.047 (1) |
V (Å3) | 2936.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.21 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Bruker Kappa APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.967, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33177, 7519, 4823 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.674 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.126, 1.01 |
No. of reflections | 7519 |
No. of parameters | 388 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.21 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···O1i | 0.97 | 2.49 | 3.352 (2) | 148 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
JS and RAN thank the management of Madura College for their encouragement and support. RRK thanks the DST, New Delhi, for funds under the fast-track scheme (grant No. SR/FT/CS-073/2009).
References
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Malonne, H., Hanuise, J. & Fontaine, J. (1998). Pharm. Pharmacol. Commun. 4, 241–243. CAS Google Scholar
Medda, S., Jaisankar, P., Manna, R. K., Pal, B., Giri, V. S. & Basu, M. K. (2003). J. Drug Target. 11, 123–128. Web of Science CrossRef PubMed CAS Google Scholar
Pearson, W. H. & Guo, L. (2001). Tetrahedron Lett. 42, 8267–8271. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sussman, J. L. & Wodak, S. J. (1973). Acta Cryst. B29, 2918–2926. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Wodak, S. J. (1975). Acta Cryst. B31, 569–573. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Indolizine derivatives have been found to possess a variety of biological activities such as anti-inflammatory (Malonne et al., 1998), antiviral (Medda et al., 2003) and anti-tumor (Pearson & Guo, 2001) activities. In view of its medicinal importance and in conjunction with our research interests, we synthesized the title compound and report here its X-ray structure.
In the title compound (Fig.1), the pyridinone ring adopts twisted half chair conformation with atoms N2 and C2 deviating by -0.355 (3)Å and 0.415 (3)Å respectively, from the mean plane defined by other atoms C3/C4/C5/C6. The sum of bond angles around N2 (332.65 (1) °) indicates a pyramidal geometry. Although the atoms C1, C2, C6 attached to the atom N2, are all in Sp2 hybridization, their different environments cause differences in bond lengths (N2-C2 (1.4467 (19) Å) and N2-C6 (1.457 (2) Å)) and in the bond angles (C1-N2-C2 (112.35 (13) °), C1-N2-C6 (111.00 (14) °) and C2-N2-C6 (109.31 (12) °)). The methyl group at position 1 of the pyridinone ring is in equatorial orientation, denoted by the torsion angle C1-N2-C6-C5 (177.38 (1) °). In the fused system , the pyrrolidine ring adopts the twisted envelope conformation with C8 atom at the flap deviating by 0.6496 (1) Å from the mean plane defined by other atoms C7/C3/C13/N1 and this orientation may be due to the intra-molecular C7—H7···O1 interaction. In the fused system the piperidine ring adopts a slightly distorted chair conformation as evident from the puckering parameters Q = 0.568 (2) Å, θ = 1.0 (2)° and Φ = 256 (11)° (Cremer & Pople, 1975). The twist of the 4-fluorobenzene ring (C52-C57) with respect to the spiro junction is denoted by the torsion angle C5-C51-C52-C57 (-49.1 (2) °). The dihedral angle between the mean plane of the pyridinone ring, defined by the atoms C2/C4/C5/C6 with the two 4-fluorobenzene rings are 87.70 (1) ° and 63.20 (1)°. The carbonyl bond length, i.e C4=O1 (1.214 (2) Å), is somewhat longer, due to C—H···O contacts. The C8—N1 bond length (1.456 (2) Å) is comparable with the CSp2—NSp2 distance found in similar structures (Sussman & Wodak, 1973; Wodak, 1975).
The structure is stabilized by intermolecular C11—H11A···O1 interactions generating chains along [101] (Fig. 2).