organic compounds
5′′-(2,4-Dichlorobenzylidene)-1′-(2,4-dichlorophenyl)-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 compound, C37H30Cl4N2O2, the pyridinone ring adopts a twisted half-chair conformation. In the octahydroindolizine fused-ring system, the piperidine ring is in a chair conformation and the pyrrole ring is twisted about the C—N bond linking the five- and six-membered rings. The molecular structure features an intramolecular C—H⋯O interaction and the crystal packing is stabilized by C—H⋯π interactions.
Related literature
For the importance of et al. (2006); Chande et al. (2005); Dandia et al. (2003); Shaharyar et al. (2006); Sriram et al. (2006). For related acenaphthylene structures, see: Hazell & Hazell (1977); Hazell & Weigelt (1976); Jones et al. (1992); Sundar et al. (2002).
see: BiavaExperimental
Crystal data
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Refinement
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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/S1600536812037956/tk5147sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037956/tk5147Isup2.hkl
A mixture of 1-methyl-3,5-bis[(E)-2,4-dichloro phenylmethylidene]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. The product was recrystallized from ethyl acetate to obtain suitable crystals of (I) for X-ray analysis having a melting point of 480 K (Yield: 96%).
H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.98 Å, and Uiso = 1.2Ueq(C) for CH2 and CH H atoms and Uiso = 1.5Ueq(C) for CH3 H atoms.
In general,
and nitrogen heterocycles display good anti-mycobacterial activities (Chande et al., 2005; Dandia et al., 2003; Sriram et al., 2006; Biava et al., 2006; Shaharyar et al., 2006) . It is also pertinent to note that the synthesis of biologically active indolizine derivatives continues to attract the attention of organic chemists, because of their wide spectrum of biological activity.In the title compound (Fig. 1) the pyridinone ring adopts twisted half-chair conformation with atoms N1 and C5 deviating by -0.638 (2) and -0.465 (2) Å, respectively, from the least-squares plane defined by the other atoms (C2/C3/C4/C6). Within the octahydroindolizine fused ring system, the piperidine ring is in a chair conformation and the pyrrole ring is twisted about the N2—C8 bond. The C—C bond lengths and C—C—C angles in the acenaphthylene group compare with those of related structures (Hazell & Hazell, 1977; Hazell & Weigelt, 1976; Jones et al., 1992; Sundar et al., 2002). The observed conformation of the pyrrole ring may be due to the presence of an intramolecular C8—H8···O2 interaction (Table 1). The dihedral angle between the dichlorobenzene rings is 67.2 (1)° and these rings form angles of 46.8 (1) and 68.6 (1)° with the acenaphthene group, respectively. The sum of the bond angles at N2 of the pyrrole ring is 337.78°, indicating sp3-hybridization.
A weak C—H···π interaction (Table 1) viz., C10—H10···Cg1 is observed (Cg1 is the centroid of the ring C32—C37).
For the importance of
see: Biava et al. (2006); Chande et al. (2005); Dandia et al. (2003); Shaharyar et al. (2006); Sriram et al. (2006). For related acenaphthylene structures, see: Hazell & Hazell (1977); Hazell & Weigelt (1976); Jones et al. (1992); Sundar et al. (2002)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. H-atoms are omitted for clarity. |
C37H30Cl4N2O2 | F(000) = 1400 |
Mr = 676.43 | Dx = 1.362 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2000 reflections |
a = 8.5695 (2) Å | θ = 2–31° |
b = 16.1634 (5) Å | µ = 0.40 mm−1 |
c = 23.8325 (7) Å | T = 293 K |
β = 92.399 (2)° | Block, colourless |
V = 3298.20 (16) Å3 | 0.23 × 0.21 × 0.19 mm |
Z = 4 |
Bruker Kappa APEXII diffractometer | 5750 independent reflections |
Radiation source: fine-focus sealed tube | 4518 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 0 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
ω and φ scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −19→19 |
Tmin = 0.967, Tmax = 0.974 | l = −28→28 |
29915 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.035P)2 + 2.1249P] where P = (Fo2 + 2Fc2)/3 |
5750 reflections | (Δ/σ)max < 0.001 |
407 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
C37H30Cl4N2O2 | V = 3298.20 (16) Å3 |
Mr = 676.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.5695 (2) Å | µ = 0.40 mm−1 |
b = 16.1634 (5) Å | T = 293 K |
c = 23.8325 (7) Å | 0.23 × 0.21 × 0.19 mm |
β = 92.399 (2)° |
Bruker Kappa APEXII diffractometer | 5750 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4518 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.974 | Rint = 0.029 |
29915 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.60 e Å−3 |
5750 reflections | Δρmin = −0.55 e Å−3 |
407 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 > σ(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 | ||
C1 | −0.1592 (3) | 0.47714 (17) | 0.28069 (11) | 0.0528 (6) | |
H1A | −0.2056 | 0.4443 | 0.3091 | 0.079* | |
H1B | −0.2226 | 0.4742 | 0.2466 | 0.079* | |
H1C | −0.1518 | 0.5336 | 0.2930 | 0.079* | |
C2 | 0.0685 (2) | 0.49258 (14) | 0.22637 (9) | 0.0412 (5) | |
H2A | 0.0701 | 0.5507 | 0.2364 | 0.049* | |
H2B | 0.0059 | 0.4866 | 0.1917 | 0.049* | |
C3 | 0.2331 (2) | 0.46418 (12) | 0.21678 (8) | 0.0345 (5) | |
C4 | 0.3245 (2) | 0.42014 (13) | 0.26274 (8) | 0.0344 (5) | |
C5 | 0.2333 (2) | 0.38735 (12) | 0.31178 (8) | 0.0301 (4) | |
C6 | 0.0974 (2) | 0.44638 (12) | 0.32082 (8) | 0.0333 (4) | |
H6A | 0.0398 | 0.4287 | 0.3529 | 0.040* | |
H6B | 0.1364 | 0.5019 | 0.3280 | 0.040* | |
C7 | 0.3420 (2) | 0.37231 (12) | 0.36537 (8) | 0.0329 (4) | |
H7 | 0.4501 | 0.3790 | 0.3542 | 0.039* | |
C8 | 0.3193 (2) | 0.28148 (13) | 0.37979 (8) | 0.0359 (5) | |
H8 | 0.2270 | 0.2756 | 0.4024 | 0.043* | |
C9 | 0.4565 (3) | 0.23864 (15) | 0.40912 (10) | 0.0499 (6) | |
H9A | 0.4741 | 0.2615 | 0.4465 | 0.060* | |
H9B | 0.5499 | 0.2476 | 0.3883 | 0.060* | |
C10 | 0.4239 (3) | 0.14666 (16) | 0.41318 (11) | 0.0603 (7) | |
H10A | 0.5147 | 0.1188 | 0.4299 | 0.072* | |
H10B | 0.3370 | 0.1376 | 0.4372 | 0.072* | |
C11 | 0.3854 (3) | 0.11052 (15) | 0.35563 (11) | 0.0566 (7) | |
H11A | 0.3583 | 0.0526 | 0.3593 | 0.068* | |
H11B | 0.4763 | 0.1142 | 0.3328 | 0.068* | |
C12 | 0.2503 (3) | 0.15664 (13) | 0.32705 (10) | 0.0468 (6) | |
H12A | 0.2310 | 0.1354 | 0.2893 | 0.056* | |
H12B | 0.1565 | 0.1486 | 0.3478 | 0.056* | |
C13 | 0.1744 (2) | 0.29741 (12) | 0.29436 (8) | 0.0324 (4) | |
C14 | 0.0011 (2) | 0.28284 (13) | 0.31192 (10) | 0.0413 (5) | |
C15 | −0.0909 (3) | 0.25445 (15) | 0.26233 (12) | 0.0519 (6) | |
C16 | 0.0097 (3) | 0.24771 (14) | 0.21835 (10) | 0.0490 (6) | |
C17 | 0.1641 (3) | 0.27180 (13) | 0.23272 (9) | 0.0387 (5) | |
C18 | 0.2754 (3) | 0.26134 (15) | 0.19449 (10) | 0.0523 (6) | |
H18 | 0.3790 | 0.2750 | 0.2032 | 0.063* | |
C19 | 0.2300 (4) | 0.22907 (17) | 0.14080 (11) | 0.0714 (9) | |
H19 | 0.3056 | 0.2220 | 0.1143 | 0.086* | |
C20 | 0.0795 (5) | 0.20812 (18) | 0.12678 (12) | 0.0804 (10) | |
H20 | 0.0542 | 0.1881 | 0.0910 | 0.097* | |
C21 | −0.0373 (4) | 0.21633 (17) | 0.16545 (13) | 0.0691 (9) | |
C22 | −0.1976 (5) | 0.1935 (2) | 0.15962 (18) | 0.1010 (14) | |
H22 | −0.2364 | 0.1722 | 0.1256 | 0.121* | |
C23 | −0.2948 (4) | 0.2021 (2) | 0.2026 (2) | 0.1132 (16) | |
H23 | −0.3991 | 0.1872 | 0.1969 | 0.136* | |
C24 | −0.2451 (3) | 0.23215 (19) | 0.25496 (17) | 0.0831 (10) | |
H24 | −0.3138 | 0.2370 | 0.2840 | 0.100* | |
C31 | 0.3044 (3) | 0.47215 (13) | 0.16838 (9) | 0.0387 (5) | |
H31 | 0.4048 | 0.4503 | 0.1681 | 0.046* | |
C32 | 0.2482 (3) | 0.51001 (14) | 0.11587 (9) | 0.0411 (5) | |
C33 | 0.1588 (3) | 0.58133 (16) | 0.11353 (10) | 0.0547 (6) | |
H33 | 0.1286 | 0.6048 | 0.1470 | 0.066* | |
C34 | 0.1126 (3) | 0.61910 (19) | 0.06375 (11) | 0.0678 (8) | |
H34 | 0.0530 | 0.6672 | 0.0636 | 0.081* | |
C35 | 0.1566 (3) | 0.58405 (18) | 0.01424 (11) | 0.0617 (7) | |
C36 | 0.2467 (4) | 0.51463 (17) | 0.01395 (10) | 0.0624 (7) | |
H36 | 0.2769 | 0.4919 | −0.0197 | 0.075* | |
C37 | 0.2923 (3) | 0.47867 (15) | 0.06447 (10) | 0.0516 (6) | |
C71 | 0.3175 (2) | 0.43159 (13) | 0.41354 (8) | 0.0352 (5) | |
C72 | 0.2167 (3) | 0.41435 (15) | 0.45610 (9) | 0.0479 (6) | |
H72 | 0.1644 | 0.3639 | 0.4554 | 0.058* | |
C73 | 0.1907 (3) | 0.46867 (16) | 0.49932 (10) | 0.0528 (6) | |
H73 | 0.1234 | 0.4546 | 0.5274 | 0.063* | |
C74 | 0.2651 (3) | 0.54342 (15) | 0.50045 (9) | 0.0466 (6) | |
C75 | 0.3684 (3) | 0.56349 (14) | 0.46038 (10) | 0.0450 (5) | |
H75 | 0.4208 | 0.6139 | 0.4617 | 0.054* | |
C76 | 0.3935 (2) | 0.50758 (13) | 0.41784 (9) | 0.0372 (5) | |
N1 | −0.00377 (18) | 0.44574 (10) | 0.27062 (7) | 0.0347 (4) | |
N2 | 0.28776 (19) | 0.24449 (10) | 0.32468 (7) | 0.0343 (4) | |
O1 | 0.46323 (17) | 0.40792 (11) | 0.25980 (6) | 0.0502 (4) | |
O2 | −0.04270 (19) | 0.28802 (10) | 0.35931 (7) | 0.0543 (4) | |
Cl1 | 0.52441 (8) | 0.53684 (4) | 0.36800 (3) | 0.05731 (18) | |
Cl2 | 0.22476 (9) | 0.61427 (5) | 0.55258 (3) | 0.0710 (2) | |
Cl3 | 0.41405 (13) | 0.39329 (5) | 0.06305 (3) | 0.0963 (3) | |
Cl4 | 0.10043 (13) | 0.63040 (7) | −0.04898 (3) | 0.1064 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0365 (12) | 0.0663 (16) | 0.0561 (15) | 0.0121 (11) | 0.0088 (11) | 0.0120 (13) |
C2 | 0.0388 (12) | 0.0477 (13) | 0.0374 (12) | 0.0057 (10) | 0.0034 (9) | 0.0070 (10) |
C3 | 0.0359 (11) | 0.0340 (11) | 0.0335 (11) | −0.0030 (9) | 0.0022 (9) | 0.0002 (9) |
C4 | 0.0336 (12) | 0.0363 (11) | 0.0334 (11) | −0.0025 (9) | 0.0020 (9) | −0.0024 (9) |
C5 | 0.0314 (10) | 0.0298 (10) | 0.0292 (10) | −0.0004 (8) | 0.0007 (8) | −0.0008 (8) |
C6 | 0.0366 (11) | 0.0310 (11) | 0.0326 (10) | 0.0017 (8) | 0.0047 (9) | −0.0002 (9) |
C7 | 0.0332 (11) | 0.0348 (11) | 0.0305 (10) | −0.0006 (8) | −0.0011 (8) | −0.0009 (9) |
C8 | 0.0420 (12) | 0.0352 (11) | 0.0303 (10) | 0.0008 (9) | −0.0004 (9) | 0.0005 (9) |
C9 | 0.0603 (15) | 0.0501 (14) | 0.0382 (12) | 0.0106 (12) | −0.0123 (11) | 0.0035 (11) |
C10 | 0.0800 (19) | 0.0476 (15) | 0.0524 (15) | 0.0169 (13) | −0.0087 (13) | 0.0122 (12) |
C11 | 0.0717 (17) | 0.0365 (13) | 0.0612 (16) | 0.0109 (12) | −0.0033 (13) | 0.0049 (12) |
C12 | 0.0572 (14) | 0.0318 (12) | 0.0511 (14) | −0.0005 (10) | −0.0007 (11) | −0.0021 (10) |
C13 | 0.0334 (11) | 0.0319 (11) | 0.0317 (10) | 0.0012 (8) | 0.0000 (8) | −0.0009 (8) |
C14 | 0.0380 (12) | 0.0295 (11) | 0.0565 (14) | 0.0002 (9) | 0.0028 (11) | −0.0023 (10) |
C15 | 0.0382 (13) | 0.0392 (13) | 0.0774 (17) | 0.0008 (10) | −0.0097 (12) | −0.0119 (12) |
C16 | 0.0562 (15) | 0.0321 (12) | 0.0565 (14) | 0.0088 (10) | −0.0228 (12) | −0.0098 (11) |
C17 | 0.0491 (13) | 0.0306 (11) | 0.0359 (11) | 0.0072 (9) | −0.0044 (10) | −0.0025 (9) |
C18 | 0.0714 (17) | 0.0435 (14) | 0.0425 (13) | 0.0094 (12) | 0.0064 (12) | −0.0054 (11) |
C19 | 0.124 (3) | 0.0498 (16) | 0.0408 (15) | 0.0223 (17) | 0.0108 (16) | −0.0073 (12) |
C20 | 0.135 (3) | 0.0565 (18) | 0.0467 (16) | 0.0218 (19) | −0.0341 (19) | −0.0194 (14) |
C21 | 0.090 (2) | 0.0474 (16) | 0.0660 (18) | 0.0200 (15) | −0.0392 (17) | −0.0195 (14) |
C22 | 0.098 (3) | 0.072 (2) | 0.126 (3) | 0.017 (2) | −0.073 (3) | −0.045 (2) |
C23 | 0.062 (2) | 0.088 (3) | 0.184 (5) | 0.0097 (19) | −0.053 (3) | −0.060 (3) |
C24 | 0.0433 (16) | 0.0658 (19) | 0.139 (3) | −0.0031 (13) | −0.0139 (17) | −0.034 (2) |
C31 | 0.0401 (12) | 0.0392 (12) | 0.0371 (11) | −0.0011 (9) | 0.0057 (9) | 0.0017 (9) |
C32 | 0.0464 (13) | 0.0440 (13) | 0.0333 (11) | −0.0033 (10) | 0.0064 (9) | 0.0041 (10) |
C33 | 0.0643 (16) | 0.0579 (16) | 0.0428 (13) | 0.0110 (13) | 0.0133 (12) | 0.0093 (12) |
C34 | 0.0735 (19) | 0.0722 (19) | 0.0583 (17) | 0.0209 (15) | 0.0104 (14) | 0.0213 (15) |
C35 | 0.0736 (18) | 0.0696 (19) | 0.0410 (14) | −0.0047 (15) | −0.0083 (13) | 0.0177 (13) |
C36 | 0.098 (2) | 0.0576 (17) | 0.0318 (13) | −0.0112 (15) | 0.0047 (13) | 0.0001 (12) |
C37 | 0.0712 (16) | 0.0455 (14) | 0.0387 (13) | −0.0027 (12) | 0.0096 (11) | 0.0024 (11) |
C71 | 0.0371 (11) | 0.0377 (12) | 0.0302 (10) | 0.0017 (9) | −0.0060 (9) | −0.0017 (9) |
C72 | 0.0546 (14) | 0.0475 (14) | 0.0422 (13) | −0.0101 (11) | 0.0071 (11) | −0.0067 (11) |
C73 | 0.0588 (15) | 0.0581 (16) | 0.0423 (13) | −0.0031 (12) | 0.0116 (11) | −0.0089 (12) |
C74 | 0.0498 (14) | 0.0498 (14) | 0.0394 (12) | 0.0084 (11) | −0.0071 (10) | −0.0132 (11) |
C75 | 0.0464 (13) | 0.0390 (12) | 0.0486 (13) | 0.0007 (10) | −0.0093 (11) | −0.0077 (10) |
C76 | 0.0364 (11) | 0.0374 (12) | 0.0372 (11) | 0.0030 (9) | −0.0050 (9) | 0.0008 (9) |
N1 | 0.0307 (9) | 0.0390 (10) | 0.0345 (9) | 0.0035 (7) | 0.0031 (7) | 0.0028 (8) |
N2 | 0.0392 (9) | 0.0288 (9) | 0.0345 (9) | 0.0026 (7) | −0.0034 (7) | −0.0013 (7) |
O1 | 0.0323 (9) | 0.0762 (12) | 0.0424 (9) | 0.0019 (8) | 0.0045 (7) | 0.0069 (8) |
O2 | 0.0505 (10) | 0.0524 (10) | 0.0617 (11) | −0.0038 (8) | 0.0217 (8) | −0.0015 (8) |
Cl1 | 0.0639 (4) | 0.0448 (3) | 0.0646 (4) | −0.0102 (3) | 0.0189 (3) | −0.0010 (3) |
Cl2 | 0.0791 (5) | 0.0718 (5) | 0.0623 (4) | 0.0039 (4) | 0.0055 (3) | −0.0346 (4) |
Cl3 | 0.1647 (9) | 0.0739 (5) | 0.0531 (4) | 0.0479 (5) | 0.0376 (5) | 0.0068 (4) |
Cl4 | 0.1384 (8) | 0.1225 (8) | 0.0564 (5) | 0.0076 (6) | −0.0180 (5) | 0.0381 (5) |
C1—N1 | 1.454 (3) | C15—C24 | 1.374 (4) |
C1—H1A | 0.9600 | C15—C16 | 1.389 (4) |
C1—H1B | 0.9600 | C16—C21 | 1.402 (3) |
C1—H1C | 0.9600 | C16—C17 | 1.408 (3) |
C2—N1 | 1.457 (3) | C17—C18 | 1.357 (3) |
C2—C3 | 1.510 (3) | C18—C19 | 1.421 (4) |
C2—H2A | 0.9700 | C18—H18 | 0.9300 |
C2—H2B | 0.9700 | C19—C20 | 1.361 (5) |
C3—C31 | 1.334 (3) | C19—H19 | 0.9300 |
C3—C4 | 1.500 (3) | C20—C21 | 1.395 (5) |
C4—O1 | 1.210 (2) | C20—H20 | 0.9300 |
C4—C5 | 1.528 (3) | C21—C22 | 1.424 (5) |
C5—C6 | 1.528 (3) | C22—C23 | 1.355 (6) |
C5—C7 | 1.568 (3) | C22—H22 | 0.9300 |
C5—C13 | 1.588 (3) | C23—C24 | 1.389 (5) |
C6—N1 | 1.448 (3) | C23—H23 | 0.9300 |
C6—H6A | 0.9700 | C24—H24 | 0.9300 |
C6—H6B | 0.9700 | C31—C32 | 1.457 (3) |
C7—C71 | 1.517 (3) | C31—H31 | 0.9300 |
C7—C8 | 1.522 (3) | C32—C33 | 1.384 (3) |
C7—H7 | 0.9800 | C32—C37 | 1.393 (3) |
C8—N2 | 1.458 (3) | C33—C34 | 1.377 (3) |
C8—C9 | 1.511 (3) | C33—H33 | 0.9300 |
C8—H8 | 0.9800 | C34—C35 | 1.376 (4) |
C9—C10 | 1.517 (4) | C34—H34 | 0.9300 |
C9—H9A | 0.9700 | C35—C36 | 1.362 (4) |
C9—H9B | 0.9700 | C35—Cl4 | 1.733 (3) |
C10—C11 | 1.514 (4) | C36—C37 | 1.379 (3) |
C10—H10A | 0.9700 | C36—H36 | 0.9300 |
C10—H10B | 0.9700 | C37—Cl3 | 1.731 (3) |
C11—C12 | 1.515 (3) | C71—C72 | 1.387 (3) |
C11—H11A | 0.9700 | C71—C76 | 1.392 (3) |
C11—H11B | 0.9700 | C72—C73 | 1.379 (3) |
C12—N2 | 1.457 (3) | C72—H72 | 0.9300 |
C12—H12A | 0.9700 | C73—C74 | 1.366 (3) |
C12—H12B | 0.9700 | C73—H73 | 0.9300 |
C13—N2 | 1.462 (3) | C74—C75 | 1.368 (3) |
C13—C17 | 1.525 (3) | C74—Cl2 | 1.735 (2) |
C13—C14 | 1.578 (3) | C75—C76 | 1.382 (3) |
C14—O2 | 1.208 (3) | C75—H75 | 0.9300 |
C14—C15 | 1.467 (3) | C76—Cl1 | 1.733 (2) |
N1—C1—H1A | 109.5 | C24—C15—C16 | 120.5 (3) |
N1—C1—H1B | 109.5 | C24—C15—C14 | 131.8 (3) |
H1A—C1—H1B | 109.5 | C16—C15—C14 | 107.7 (2) |
N1—C1—H1C | 109.5 | C15—C16—C21 | 122.9 (3) |
H1A—C1—H1C | 109.5 | C15—C16—C17 | 113.7 (2) |
H1B—C1—H1C | 109.5 | C21—C16—C17 | 123.4 (3) |
N1—C2—C3 | 112.30 (17) | C18—C17—C16 | 118.8 (2) |
N1—C2—H2A | 109.1 | C18—C17—C13 | 131.8 (2) |
C3—C2—H2A | 109.1 | C16—C17—C13 | 108.99 (19) |
N1—C2—H2B | 109.1 | C17—C18—C19 | 118.5 (3) |
C3—C2—H2B | 109.1 | C17—C18—H18 | 120.8 |
H2A—C2—H2B | 107.9 | C19—C18—H18 | 120.8 |
C31—C3—C4 | 115.66 (18) | C20—C19—C18 | 122.2 (3) |
C31—C3—C2 | 124.5 (2) | C20—C19—H19 | 118.9 |
C4—C3—C2 | 119.79 (17) | C18—C19—H19 | 118.9 |
O1—C4—C3 | 121.33 (18) | C19—C20—C21 | 120.8 (3) |
O1—C4—C5 | 121.55 (18) | C19—C20—H20 | 119.6 |
C3—C4—C5 | 117.04 (16) | C21—C20—H20 | 119.6 |
C6—C5—C4 | 108.00 (16) | C20—C21—C16 | 116.2 (3) |
C6—C5—C7 | 114.36 (15) | C20—C21—C22 | 128.8 (3) |
C4—C5—C7 | 111.76 (16) | C16—C21—C22 | 114.9 (3) |
C6—C5—C13 | 111.90 (16) | C23—C22—C21 | 121.4 (3) |
C4—C5—C13 | 106.54 (15) | C23—C22—H22 | 119.3 |
C7—C5—C13 | 104.03 (15) | C21—C22—H22 | 119.3 |
N1—C6—C5 | 108.20 (15) | C22—C23—C24 | 122.7 (3) |
N1—C6—H6A | 110.1 | C22—C23—H23 | 118.7 |
C5—C6—H6A | 110.1 | C24—C23—H23 | 118.7 |
N1—C6—H6B | 110.1 | C15—C24—C23 | 117.6 (3) |
C5—C6—H6B | 110.1 | C15—C24—H24 | 121.2 |
H6A—C6—H6B | 108.4 | C23—C24—H24 | 121.2 |
C71—C7—C8 | 114.53 (16) | C3—C31—C32 | 129.5 (2) |
C71—C7—C5 | 114.96 (16) | C3—C31—H31 | 115.2 |
C8—C7—C5 | 104.84 (16) | C32—C31—H31 | 115.2 |
C71—C7—H7 | 107.4 | C33—C32—C37 | 116.0 (2) |
C8—C7—H7 | 107.4 | C33—C32—C31 | 123.2 (2) |
C5—C7—H7 | 107.4 | C37—C32—C31 | 120.7 (2) |
N2—C8—C9 | 109.89 (17) | C34—C33—C32 | 122.9 (2) |
N2—C8—C7 | 102.28 (15) | C34—C33—H33 | 118.6 |
C9—C8—C7 | 116.24 (18) | C32—C33—H33 | 118.6 |
N2—C8—H8 | 109.4 | C35—C34—C33 | 118.5 (3) |
C9—C8—H8 | 109.4 | C35—C34—H34 | 120.8 |
C7—C8—H8 | 109.4 | C33—C34—H34 | 120.8 |
C8—C9—C10 | 109.7 (2) | C36—C35—C34 | 121.3 (2) |
C8—C9—H9A | 109.7 | C36—C35—Cl4 | 119.3 (2) |
C10—C9—H9A | 109.7 | C34—C35—Cl4 | 119.4 (2) |
C8—C9—H9B | 109.7 | C35—C36—C37 | 118.9 (2) |
C10—C9—H9B | 109.7 | C35—C36—H36 | 120.6 |
H9A—C9—H9B | 108.2 | C37—C36—H36 | 120.6 |
C11—C10—C9 | 110.7 (2) | C36—C37—C32 | 122.5 (2) |
C11—C10—H10A | 109.5 | C36—C37—Cl3 | 117.91 (19) |
C9—C10—H10A | 109.5 | C32—C37—Cl3 | 119.55 (19) |
C11—C10—H10B | 109.5 | C72—C71—C76 | 115.28 (19) |
C9—C10—H10B | 109.5 | C72—C71—C7 | 122.47 (19) |
H10A—C10—H10B | 108.1 | C76—C71—C7 | 122.25 (18) |
C10—C11—C12 | 110.5 (2) | C73—C72—C71 | 122.9 (2) |
C10—C11—H11A | 109.5 | C73—C72—H72 | 118.5 |
C12—C11—H11A | 109.5 | C71—C72—H72 | 118.5 |
C10—C11—H11B | 109.5 | C74—C73—C72 | 119.2 (2) |
C12—C11—H11B | 109.5 | C74—C73—H73 | 120.4 |
H11A—C11—H11B | 108.1 | C72—C73—H73 | 120.4 |
N2—C12—C11 | 109.34 (19) | C73—C74—C75 | 120.7 (2) |
N2—C12—H12A | 109.8 | C73—C74—Cl2 | 119.40 (19) |
C11—C12—H12A | 109.8 | C75—C74—Cl2 | 119.85 (19) |
N2—C12—H12B | 109.8 | C74—C75—C76 | 118.8 (2) |
C11—C12—H12B | 109.8 | C74—C75—H75 | 120.6 |
H12A—C12—H12B | 108.3 | C76—C75—H75 | 120.6 |
N2—C13—C17 | 109.14 (16) | C75—C76—C71 | 123.0 (2) |
N2—C13—C14 | 113.25 (16) | C75—C76—Cl1 | 116.72 (17) |
C17—C13—C14 | 101.40 (16) | C71—C76—Cl1 | 120.31 (16) |
N2—C13—C5 | 102.07 (15) | C6—N1—C1 | 112.44 (17) |
C17—C13—C5 | 120.34 (16) | C6—N1—C2 | 109.68 (16) |
C14—C13—C5 | 111.06 (15) | C1—N1—C2 | 110.96 (17) |
O2—C14—C15 | 126.7 (2) | C12—N2—C8 | 113.42 (17) |
O2—C14—C13 | 124.8 (2) | C12—N2—C13 | 116.49 (17) |
C15—C14—C13 | 108.24 (19) | C8—N2—C13 | 107.43 (15) |
N1—C2—C3—C31 | 153.9 (2) | C17—C18—C19—C20 | −0.3 (4) |
N1—C2—C3—C4 | −23.0 (3) | C18—C19—C20—C21 | −1.1 (4) |
C31—C3—C4—O1 | 14.3 (3) | C19—C20—C21—C16 | 0.6 (4) |
C2—C3—C4—O1 | −168.5 (2) | C19—C20—C21—C22 | −176.1 (3) |
C31—C3—C4—C5 | −162.48 (18) | C15—C16—C21—C20 | −175.8 (2) |
C2—C3—C4—C5 | 14.7 (3) | C17—C16—C21—C20 | 1.3 (4) |
O1—C4—C5—C6 | 150.4 (2) | C15—C16—C21—C22 | 1.4 (4) |
C3—C4—C5—C6 | −32.8 (2) | C17—C16—C21—C22 | 178.5 (2) |
O1—C4—C5—C7 | 23.8 (3) | C20—C21—C22—C23 | 176.7 (4) |
C3—C4—C5—C7 | −159.43 (17) | C16—C21—C22—C23 | 0.0 (5) |
O1—C4—C5—C13 | −89.2 (2) | C21—C22—C23—C24 | −1.0 (6) |
C3—C4—C5—C13 | 87.6 (2) | C16—C15—C24—C23 | 0.8 (4) |
C4—C5—C6—N1 | 62.4 (2) | C14—C15—C24—C23 | −175.6 (3) |
C7—C5—C6—N1 | −172.48 (15) | C22—C23—C24—C15 | 0.6 (6) |
C13—C5—C6—N1 | −54.5 (2) | C4—C3—C31—C32 | 179.0 (2) |
C6—C5—C7—C71 | −12.6 (2) | C2—C3—C31—C32 | 1.9 (4) |
C4—C5—C7—C71 | 110.51 (19) | C3—C31—C32—C33 | 38.4 (4) |
C13—C5—C7—C71 | −134.93 (17) | C3—C31—C32—C37 | −146.3 (2) |
C6—C5—C7—C8 | 114.08 (18) | C37—C32—C33—C34 | 1.2 (4) |
C4—C5—C7—C8 | −122.83 (17) | C31—C32—C33—C34 | 176.7 (2) |
C13—C5—C7—C8 | −8.27 (19) | C32—C33—C34—C35 | 0.4 (4) |
C71—C7—C8—N2 | 158.36 (16) | C33—C34—C35—C36 | −1.4 (5) |
C5—C7—C8—N2 | 31.43 (19) | C33—C34—C35—Cl4 | −179.9 (2) |
C71—C7—C8—C9 | −81.9 (2) | C34—C35—C36—C37 | 0.8 (4) |
C5—C7—C8—C9 | 151.13 (18) | Cl4—C35—C36—C37 | 179.3 (2) |
N2—C8—C9—C10 | −56.6 (2) | C35—C36—C37—C32 | 0.8 (4) |
C7—C8—C9—C10 | −172.14 (19) | C35—C36—C37—Cl3 | −177.1 (2) |
C8—C9—C10—C11 | 55.6 (3) | C33—C32—C37—C36 | −1.8 (4) |
C9—C10—C11—C12 | −55.5 (3) | C31—C32—C37—C36 | −177.4 (2) |
C10—C11—C12—N2 | 55.8 (3) | C33—C32—C37—Cl3 | 176.12 (19) |
C6—C5—C13—N2 | −141.69 (16) | C31—C32—C37—Cl3 | 0.5 (3) |
C4—C5—C13—N2 | 100.49 (17) | C8—C7—C71—C72 | −29.0 (3) |
C7—C5—C13—N2 | −17.73 (18) | C5—C7—C71—C72 | 92.5 (2) |
C6—C5—C13—C17 | 97.4 (2) | C8—C7—C71—C76 | 151.57 (19) |
C4—C5—C13—C17 | −20.4 (2) | C5—C7—C71—C76 | −86.9 (2) |
C7—C5—C13—C17 | −138.64 (17) | C76—C71—C72—C73 | 1.0 (3) |
C6—C5—C13—C14 | −20.7 (2) | C7—C71—C72—C73 | −178.4 (2) |
C4—C5—C13—C14 | −138.51 (17) | C71—C72—C73—C74 | 0.9 (4) |
C7—C5—C13—C14 | 103.27 (18) | C72—C73—C74—C75 | −2.2 (4) |
N2—C13—C14—O2 | 56.1 (3) | C72—C73—C74—Cl2 | 176.50 (19) |
C17—C13—C14—O2 | 172.9 (2) | C73—C74—C75—C76 | 1.5 (4) |
C5—C13—C14—O2 | −58.1 (3) | Cl2—C74—C75—C76 | −177.16 (17) |
N2—C13—C14—C15 | −118.41 (19) | C74—C75—C76—C71 | 0.5 (3) |
C17—C13—C14—C15 | −1.6 (2) | C74—C75—C76—Cl1 | 179.48 (17) |
C5—C13—C14—C15 | 127.42 (18) | C72—C71—C76—C75 | −1.7 (3) |
O2—C14—C15—C24 | 4.5 (4) | C7—C71—C76—C75 | 177.69 (19) |
C13—C14—C15—C24 | 178.9 (3) | C72—C71—C76—Cl1 | 179.33 (17) |
O2—C14—C15—C16 | −172.1 (2) | C7—C71—C76—Cl1 | −1.2 (3) |
C13—C14—C15—C16 | 2.2 (2) | C5—C6—N1—C1 | 161.08 (17) |
C24—C15—C16—C21 | −1.8 (4) | C5—C6—N1—C2 | −74.95 (19) |
C14—C15—C16—C21 | 175.3 (2) | C3—C2—N1—C6 | 52.4 (2) |
C24—C15—C16—C17 | −179.1 (2) | C3—C2—N1—C1 | 177.25 (19) |
C14—C15—C16—C17 | −2.0 (3) | C11—C12—N2—C8 | −59.1 (2) |
C15—C16—C17—C18 | 174.6 (2) | C11—C12—N2—C13 | 175.37 (18) |
C21—C16—C17—C18 | −2.7 (3) | C9—C8—N2—C12 | 60.0 (2) |
C15—C16—C17—C13 | 0.9 (3) | C7—C8—N2—C12 | −175.93 (17) |
C21—C16—C17—C13 | −176.4 (2) | C9—C8—N2—C13 | −169.77 (17) |
N2—C13—C17—C18 | −52.3 (3) | C7—C8—N2—C13 | −45.73 (19) |
C14—C13—C17—C18 | −172.1 (2) | C17—C13—N2—C12 | −63.5 (2) |
C5—C13—C17—C18 | 65.0 (3) | C14—C13—N2—C12 | 48.6 (2) |
N2—C13—C17—C16 | 120.24 (18) | C5—C13—N2—C12 | 168.11 (17) |
C14—C13—C17—C16 | 0.5 (2) | C17—C13—N2—C8 | 168.05 (16) |
C5—C13—C17—C16 | −122.4 (2) | C14—C13—N2—C8 | −79.8 (2) |
C16—C17—C18—C19 | 2.1 (3) | C5—C13—N2—C8 | 39.66 (18) |
C13—C17—C18—C19 | 174.1 (2) |
Cg1 is the centroid of the C32–C37 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O2 | 0.98 | 2.50 | 3.122 (3) | 121 |
C10—H10a···Cg1i | 0.97 | 2.68 | 3.5969 | 158 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C37H30Cl4N2O2 |
Mr | 676.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.5695 (2), 16.1634 (5), 23.8325 (7) |
β (°) | 92.399 (2) |
V (Å3) | 3298.20 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.23 × 0.21 × 0.19 |
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 | 29915, 5750, 4518 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.105, 1.08 |
No. of reflections | 5750 |
No. of parameters | 407 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.55 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Cg1 is the centroid of the C32–C37 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O2 | 0.98 | 2.50 | 3.122 (3) | 121 |
C10—H10a···Cg1i | 0.97 | 2.68 | 3.5969 | 158 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Acknowledgements
JS thanks the UGC for the FIST support. JS and RV thank the management of Madura College for their encouragement and support. RRK thanks the DST, New Delhi, for funds under the fast-track scheme (No. SR/FT/CS-073/2009).
References
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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.
In general, spiro compounds and nitrogen heterocycles display good anti-mycobacterial activities (Chande et al., 2005; Dandia et al., 2003; Sriram et al., 2006; Biava et al., 2006; Shaharyar et al., 2006) . It is also pertinent to note that the synthesis of biologically active indolizine derivatives continues to attract the attention of organic chemists, because of their wide spectrum of biological activity.
In the title compound (Fig. 1) the pyridinone ring adopts twisted half-chair conformation with atoms N1 and C5 deviating by -0.638 (2) and -0.465 (2) Å, respectively, from the least-squares plane defined by the other atoms (C2/C3/C4/C6). Within the octahydroindolizine fused ring system, the piperidine ring is in a chair conformation and the pyrrole ring is twisted about the N2—C8 bond. The C—C bond lengths and C—C—C angles in the acenaphthylene group compare with those of related structures (Hazell & Hazell, 1977; Hazell & Weigelt, 1976; Jones et al., 1992; Sundar et al., 2002). The observed conformation of the pyrrole ring may be due to the presence of an intramolecular C8—H8···O2 interaction (Table 1). The dihedral angle between the dichlorobenzene rings is 67.2 (1)° and these rings form angles of 46.8 (1) and 68.6 (1)° with the acenaphthene group, respectively. The sum of the bond angles at N2 of the pyrrole ring is 337.78°, indicating sp3-hybridization.
A weak C—H···π interaction (Table 1) viz., C10—H10···Cg1 is observed (Cg1 is the centroid of the ring C32—C37).