organic compounds
5′′-(4-Chlorobenzylidene)-1′-(4-chlorophenyl)-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, C37H32Cl2N2O2, the pyridinone ring adopts a twisted half-chair conformation. The fused pyrrolidine and piperidine rings of the octahydroindolizine unit exhibit envelope (with the C atom bound to the C atom bearing the chlorobenzene ring being the flap atom) and chair conformations, respectively. The dihedral angle between the chlorobenzene rings is 84.03 (1)°. In the crystal, C—H⋯π interactions lead to supramolecular chains along [101] that assemble in the ac plane. Connections along the b axis are of the type Cl⋯Cl [3.4065 (8) Å].
Related literature
For general properties of indolizines, see: Gundersen et al. (2007). For related structures, see: Sussman & Wodak (1973); Wodak (1975). For ring conformation analysis, see: Cremer & Pople (1975).
Experimental
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
10.1107/S160053681204545X/tk5167sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681204545X/tk5167Isup2.hkl
A mixture of 1-methyl-3,5-bis[(E)-4-cholromethylidene]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: 518 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 (-1 0 1) reflection was probably affected by the beam-stop and was omitted from the refinement.
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 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms have been omitted. |
C37H32Cl2N2O2 | F(000) = 1272 |
Mr = 607.55 | Dx = 1.319 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2000 reflections |
a = 14.1346 (5) Å | θ = 2–31° |
b = 15.2184 (6) Å | µ = 0.25 mm−1 |
c = 14.5603 (6) Å | T = 293 K |
β = 102.337 (1)° | Block, yellow |
V = 3059.7 (2) Å3 | 0.21 × 0.19 × 0.18 mm |
Z = 4 |
Bruker Kappa APEXII diffractometer | 7321 independent reflections |
Radiation source: fine-focus sealed tube | 4492 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 0 pixels mm-1 | θmax = 27.9°, θmin = 2.0° |
ω and ϕ scans | h = −18→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −16→20 |
Tmin = 0.967, Tmax = 0.974 | l = −19→17 |
32144 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.7517P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
7321 reflections | Δρmax = 0.23 e Å−3 |
389 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0023 (4) |
C37H32Cl2N2O2 | V = 3059.7 (2) Å3 |
Mr = 607.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.1346 (5) Å | µ = 0.25 mm−1 |
b = 15.2184 (6) Å | T = 293 K |
c = 14.5603 (6) Å | 0.21 × 0.19 × 0.18 mm |
β = 102.337 (1)° |
Bruker Kappa APEXII diffractometer | 7321 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4492 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.974 | Rint = 0.041 |
32144 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.23 e Å−3 |
7321 reflections | Δρmin = −0.38 e Å−3 |
389 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 | ||
Cl1 | 0.04645 (4) | 0.07200 (4) | 0.43166 (3) | 0.07029 (19) | |
Cl2 | 0.71789 (5) | 0.05345 (6) | −0.16446 (6) | 0.1089 (3) | |
O1 | 0.13905 (9) | 0.07134 (8) | −0.05296 (10) | 0.0538 (4) | |
N1 | −0.00938 (10) | 0.28748 (10) | −0.08843 (9) | 0.0402 (4) | |
O2 | 0.13090 (10) | 0.42902 (8) | −0.00055 (9) | 0.0547 (4) | |
C16 | 0.18467 (12) | 0.32304 (11) | −0.19504 (12) | 0.0380 (4) | |
C7 | 0.03322 (12) | 0.19119 (11) | 0.03419 (11) | 0.0368 (4) | |
H7 | 0.0063 | 0.1416 | −0.0060 | 0.044* | |
C13 | 0.09576 (12) | 0.28443 (11) | −0.07824 (11) | 0.0356 (4) | |
N2 | 0.28362 (10) | 0.29147 (10) | 0.05353 (10) | 0.0421 (4) | |
C4 | 0.18149 (13) | 0.13902 (12) | −0.02618 (11) | 0.0383 (4) | |
C6 | 0.34414 (13) | 0.21861 (13) | 0.03624 (14) | 0.0487 (5) | |
H6A | 0.3748 | 0.1921 | 0.0958 | 0.058* | |
H6B | 0.3948 | 0.2407 | 0.0068 | 0.058* | |
C71 | 0.04004 (12) | 0.16261 (11) | 0.13512 (11) | 0.0371 (4) | |
C51 | 0.32365 (14) | 0.09841 (12) | −0.08389 (13) | 0.0473 (5) | |
H51 | 0.2793 | 0.0603 | −0.1200 | 0.057* | |
C21 | 0.22039 (13) | 0.31929 (13) | −0.27798 (13) | 0.0463 (5) | |
C3 | 0.12964 (12) | 0.21704 (11) | 0.00698 (11) | 0.0349 (4) | |
C17 | 0.12068 (12) | 0.26047 (11) | −0.17163 (11) | 0.0363 (4) | |
C14 | 0.14749 (13) | 0.37636 (12) | −0.05770 (12) | 0.0413 (4) | |
C74 | 0.04679 (13) | 0.10710 (13) | 0.31784 (12) | 0.0453 (5) | |
C8 | −0.03173 (12) | 0.26980 (12) | 0.00271 (12) | 0.0411 (4) | |
H8 | −0.0113 | 0.3195 | 0.0451 | 0.049* | |
C15 | 0.20574 (12) | 0.39111 (12) | −0.12968 (12) | 0.0407 (4) | |
C72 | 0.05102 (14) | 0.07488 (12) | 0.15926 (13) | 0.0458 (5) | |
H72 | 0.0557 | 0.0337 | 0.1132 | 0.055* | |
C2 | 0.20079 (12) | 0.26003 (12) | 0.08805 (12) | 0.0406 (4) | |
H2A | 0.1698 | 0.3087 | 0.1130 | 0.049* | |
H2B | 0.2216 | 0.2177 | 0.1381 | 0.049* | |
C5 | 0.28707 (13) | 0.14998 (11) | −0.02579 (12) | 0.0397 (4) | |
C52 | 0.42240 (14) | 0.09202 (12) | −0.10001 (14) | 0.0476 (5) | |
C19 | 0.12123 (15) | 0.19024 (14) | −0.31828 (13) | 0.0529 (5) | |
H19 | 0.0987 | 0.1454 | −0.3607 | 0.064* | |
C24 | 0.26740 (14) | 0.45710 (13) | −0.14340 (15) | 0.0506 (5) | |
H24 | 0.2822 | 0.5033 | −0.1010 | 0.061* | |
C76 | 0.03301 (15) | 0.22134 (13) | 0.20577 (12) | 0.0515 (5) | |
H76 | 0.0262 | 0.2809 | 0.1915 | 0.062* | |
C20 | 0.18534 (15) | 0.24935 (14) | −0.33970 (14) | 0.0552 (5) | |
H20 | 0.2064 | 0.2437 | −0.3957 | 0.066* | |
C23 | 0.30756 (14) | 0.45261 (15) | −0.22372 (17) | 0.0592 (6) | |
H23 | 0.3514 | 0.4958 | −0.2325 | 0.071* | |
C12 | −0.06134 (14) | 0.36225 (14) | −0.13800 (14) | 0.0563 (5) | |
H12A | −0.0443 | 0.3692 | −0.1987 | 0.068* | |
H12B | −0.0434 | 0.4156 | −0.1020 | 0.068* | |
C18 | 0.08774 (13) | 0.19465 (12) | −0.23358 (12) | 0.0439 (4) | |
H18 | 0.0440 | 0.1533 | −0.2204 | 0.053* | |
C73 | 0.05515 (14) | 0.04700 (13) | 0.25014 (13) | 0.0502 (5) | |
H73 | 0.0636 | −0.0123 | 0.2653 | 0.060* | |
C75 | 0.03572 (15) | 0.19436 (13) | 0.29690 (13) | 0.0531 (5) | |
H75 | 0.0301 | 0.2350 | 0.3431 | 0.064* | |
C55 | 0.60436 (16) | 0.06903 (14) | −0.13949 (18) | 0.0621 (6) | |
C54 | 0.52339 (17) | 0.05391 (14) | −0.20863 (17) | 0.0667 (6) | |
H54 | 0.5292 | 0.0367 | −0.2684 | 0.080* | |
C9 | −0.13872 (14) | 0.25407 (15) | −0.00761 (15) | 0.0601 (6) | |
H9A | −0.1533 | 0.2466 | 0.0541 | 0.072* | |
H9B | −0.1569 | 0.2005 | −0.0431 | 0.072* | |
C22 | 0.28499 (14) | 0.38774 (15) | −0.28913 (15) | 0.0565 (6) | |
H22 | 0.3123 | 0.3884 | −0.3418 | 0.068* | |
C1 | 0.33930 (15) | 0.35679 (14) | 0.11492 (15) | 0.0615 (6) | |
H1A | 0.3930 | 0.3756 | 0.0891 | 0.092* | |
H1B | 0.3629 | 0.3317 | 0.1760 | 0.092* | |
H1C | 0.2988 | 0.4063 | 0.1203 | 0.092* | |
C53 | 0.43343 (16) | 0.06461 (14) | −0.18817 (16) | 0.0615 (6) | |
H53 | 0.3785 | 0.0532 | −0.2346 | 0.074* | |
C57 | 0.50604 (15) | 0.10706 (13) | −0.03210 (14) | 0.0534 (5) | |
H57 | 0.5010 | 0.1252 | 0.0277 | 0.064* | |
C10 | −0.19697 (16) | 0.33041 (18) | −0.05758 (16) | 0.0737 (7) | |
H10A | −0.1842 | 0.3828 | −0.0190 | 0.088* | |
H10B | −0.2656 | 0.3173 | −0.0675 | 0.088* | |
C56 | 0.59666 (15) | 0.09545 (14) | −0.05184 (16) | 0.0586 (5) | |
H56 | 0.6521 | 0.1056 | −0.0056 | 0.070* | |
C11 | −0.16993 (15) | 0.34676 (18) | −0.15152 (15) | 0.0703 (7) | |
H11A | −0.2047 | 0.3977 | −0.1814 | 0.084* | |
H11B | −0.1885 | 0.2965 | −0.1923 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0784 (4) | 0.0908 (4) | 0.0412 (3) | −0.0074 (3) | 0.0117 (3) | 0.0230 (3) |
Cl2 | 0.0596 (4) | 0.1353 (7) | 0.1435 (7) | −0.0031 (4) | 0.0477 (4) | −0.0432 (6) |
O1 | 0.0486 (8) | 0.0433 (8) | 0.0701 (9) | −0.0097 (7) | 0.0140 (7) | −0.0120 (7) |
N1 | 0.0354 (8) | 0.0510 (9) | 0.0346 (7) | 0.0028 (7) | 0.0082 (6) | 0.0081 (7) |
O2 | 0.0640 (9) | 0.0452 (8) | 0.0559 (8) | −0.0004 (7) | 0.0152 (7) | −0.0112 (7) |
C16 | 0.0324 (9) | 0.0422 (10) | 0.0396 (9) | 0.0029 (8) | 0.0079 (7) | 0.0080 (8) |
C7 | 0.0370 (9) | 0.0413 (10) | 0.0322 (8) | −0.0053 (8) | 0.0074 (7) | −0.0008 (7) |
C13 | 0.0367 (9) | 0.0390 (10) | 0.0316 (8) | −0.0041 (8) | 0.0081 (7) | 0.0004 (7) |
N2 | 0.0378 (8) | 0.0436 (9) | 0.0435 (8) | −0.0079 (7) | 0.0058 (7) | −0.0082 (7) |
C4 | 0.0404 (10) | 0.0388 (10) | 0.0343 (9) | −0.0014 (9) | 0.0048 (8) | 0.0023 (8) |
C6 | 0.0378 (10) | 0.0545 (12) | 0.0521 (11) | −0.0036 (9) | 0.0061 (8) | −0.0059 (10) |
C71 | 0.0362 (9) | 0.0411 (10) | 0.0346 (9) | −0.0059 (8) | 0.0086 (7) | 0.0028 (8) |
C51 | 0.0434 (11) | 0.0448 (11) | 0.0533 (11) | −0.0020 (9) | 0.0091 (9) | −0.0037 (9) |
C21 | 0.0392 (10) | 0.0571 (12) | 0.0450 (10) | 0.0081 (9) | 0.0148 (8) | 0.0119 (9) |
C3 | 0.0358 (9) | 0.0383 (9) | 0.0300 (8) | −0.0033 (8) | 0.0060 (7) | 0.0007 (7) |
C17 | 0.0356 (9) | 0.0415 (10) | 0.0316 (8) | −0.0004 (8) | 0.0068 (7) | 0.0029 (8) |
C14 | 0.0420 (10) | 0.0400 (10) | 0.0402 (9) | 0.0005 (9) | 0.0052 (8) | 0.0009 (8) |
C74 | 0.0402 (10) | 0.0591 (12) | 0.0360 (9) | −0.0073 (9) | 0.0066 (8) | 0.0123 (9) |
C8 | 0.0396 (10) | 0.0507 (11) | 0.0339 (9) | 0.0000 (9) | 0.0101 (8) | 0.0047 (8) |
C15 | 0.0363 (10) | 0.0388 (10) | 0.0458 (10) | −0.0006 (8) | 0.0060 (8) | 0.0079 (8) |
C72 | 0.0511 (11) | 0.0423 (11) | 0.0446 (10) | 0.0017 (9) | 0.0116 (9) | 0.0008 (9) |
C2 | 0.0392 (10) | 0.0473 (11) | 0.0341 (9) | −0.0033 (9) | 0.0051 (7) | −0.0004 (8) |
C5 | 0.0371 (10) | 0.0389 (10) | 0.0419 (9) | −0.0004 (8) | 0.0055 (8) | 0.0015 (8) |
C52 | 0.0468 (11) | 0.0393 (10) | 0.0583 (12) | 0.0012 (9) | 0.0149 (9) | −0.0043 (9) |
C19 | 0.0588 (13) | 0.0590 (13) | 0.0412 (10) | 0.0016 (11) | 0.0111 (9) | −0.0087 (9) |
C24 | 0.0432 (11) | 0.0438 (11) | 0.0622 (12) | −0.0055 (9) | 0.0053 (10) | 0.0086 (10) |
C76 | 0.0779 (15) | 0.0398 (11) | 0.0392 (10) | −0.0039 (10) | 0.0176 (10) | 0.0036 (8) |
C20 | 0.0577 (13) | 0.0709 (14) | 0.0423 (11) | 0.0082 (11) | 0.0229 (10) | −0.0013 (10) |
C23 | 0.0380 (11) | 0.0579 (13) | 0.0840 (16) | −0.0038 (10) | 0.0184 (11) | 0.0239 (12) |
C12 | 0.0519 (12) | 0.0691 (14) | 0.0478 (11) | 0.0115 (11) | 0.0100 (9) | 0.0183 (10) |
C18 | 0.0462 (11) | 0.0493 (11) | 0.0358 (9) | −0.0052 (9) | 0.0080 (8) | −0.0011 (8) |
C73 | 0.0538 (12) | 0.0428 (11) | 0.0526 (11) | 0.0027 (10) | 0.0079 (9) | 0.0149 (9) |
C75 | 0.0709 (14) | 0.0540 (12) | 0.0365 (10) | −0.0066 (11) | 0.0159 (10) | −0.0019 (9) |
C55 | 0.0493 (13) | 0.0520 (13) | 0.0901 (17) | 0.0005 (11) | 0.0260 (12) | −0.0113 (12) |
C54 | 0.0667 (15) | 0.0624 (14) | 0.0772 (15) | −0.0058 (12) | 0.0289 (13) | −0.0253 (12) |
C9 | 0.0394 (11) | 0.0851 (16) | 0.0581 (12) | 0.0032 (11) | 0.0157 (9) | 0.0171 (12) |
C22 | 0.0424 (11) | 0.0698 (14) | 0.0638 (13) | 0.0049 (11) | 0.0259 (10) | 0.0193 (12) |
C1 | 0.0508 (12) | 0.0633 (14) | 0.0671 (13) | −0.0151 (11) | 0.0050 (10) | −0.0207 (11) |
C53 | 0.0512 (13) | 0.0642 (14) | 0.0698 (14) | −0.0068 (11) | 0.0146 (11) | −0.0224 (11) |
C57 | 0.0506 (12) | 0.0555 (13) | 0.0539 (12) | 0.0084 (10) | 0.0104 (10) | 0.0011 (10) |
C10 | 0.0420 (12) | 0.109 (2) | 0.0717 (15) | 0.0186 (13) | 0.0155 (11) | 0.0181 (14) |
C56 | 0.0438 (12) | 0.0599 (13) | 0.0708 (14) | 0.0061 (10) | 0.0093 (10) | −0.0020 (11) |
C11 | 0.0470 (13) | 0.0984 (18) | 0.0625 (13) | 0.0161 (13) | 0.0048 (10) | 0.0231 (13) |
Cl1—C74 | 1.7422 (17) | C72—H72 | 0.9300 |
Cl2—C55 | 1.736 (2) | C2—H2A | 0.9700 |
O1—C4 | 1.214 (2) | C2—H2B | 0.9700 |
N1—C8 | 1.454 (2) | C52—C57 | 1.389 (3) |
N1—C12 | 1.459 (2) | C52—C53 | 1.390 (3) |
N1—C13 | 1.462 (2) | C19—C20 | 1.360 (3) |
O2—C14 | 1.214 (2) | C19—C18 | 1.414 (2) |
C16—C15 | 1.395 (2) | C19—H19 | 0.9300 |
C16—C17 | 1.405 (2) | C24—C23 | 1.407 (3) |
C16—C21 | 1.406 (2) | C24—H24 | 0.9300 |
C7—C71 | 1.516 (2) | C76—C75 | 1.382 (2) |
C7—C8 | 1.518 (2) | C76—H76 | 0.9300 |
C7—C3 | 1.549 (2) | C20—H20 | 0.9300 |
C7—H7 | 0.9800 | C23—C22 | 1.361 (3) |
C13—C17 | 1.520 (2) | C23—H23 | 0.9300 |
C13—C14 | 1.577 (2) | C12—C11 | 1.524 (3) |
C13—C3 | 1.602 (2) | C12—H12A | 0.9700 |
N2—C2 | 1.450 (2) | C12—H12B | 0.9700 |
N2—C1 | 1.451 (2) | C18—H18 | 0.9300 |
N2—C6 | 1.455 (2) | C73—H73 | 0.9300 |
C4—C5 | 1.500 (2) | C75—H75 | 0.9300 |
C4—C3 | 1.527 (2) | C55—C56 | 1.364 (3) |
C6—C5 | 1.499 (2) | C55—C54 | 1.373 (3) |
C6—H6A | 0.9700 | C54—C53 | 1.376 (3) |
C6—H6B | 0.9700 | C54—H54 | 0.9300 |
C71—C72 | 1.381 (2) | C9—C10 | 1.517 (3) |
C71—C76 | 1.382 (2) | C9—H9A | 0.9700 |
C51—C5 | 1.336 (2) | C9—H9B | 0.9700 |
C51—C52 | 1.467 (3) | C22—H22 | 0.9300 |
C51—H51 | 0.9300 | C1—H1A | 0.9600 |
C21—C20 | 1.413 (3) | C1—H1B | 0.9600 |
C21—C22 | 1.417 (3) | C1—H1C | 0.9600 |
C3—C2 | 1.525 (2) | C53—H53 | 0.9300 |
C17—C18 | 1.362 (2) | C57—C56 | 1.383 (3) |
C14—C15 | 1.482 (2) | C57—H57 | 0.9300 |
C74—C75 | 1.364 (3) | C10—C11 | 1.517 (3) |
C74—C73 | 1.368 (3) | C10—H10A | 0.9700 |
C8—C9 | 1.507 (3) | C10—H10B | 0.9700 |
C8—H8 | 0.9800 | C56—H56 | 0.9300 |
C15—C24 | 1.372 (2) | C11—H11A | 0.9700 |
C72—C73 | 1.379 (2) | C11—H11B | 0.9700 |
C8—N1—C12 | 114.29 (14) | C57—C52—C53 | 117.44 (18) |
C8—N1—C13 | 108.41 (13) | C57—C52—C51 | 124.71 (18) |
C12—N1—C13 | 117.92 (14) | C53—C52—C51 | 117.77 (18) |
C15—C16—C17 | 113.11 (15) | C20—C19—C18 | 122.18 (19) |
C15—C16—C21 | 123.54 (16) | C20—C19—H19 | 118.9 |
C17—C16—C21 | 123.29 (17) | C18—C19—H19 | 118.9 |
C71—C7—C8 | 115.34 (14) | C15—C24—C23 | 117.86 (19) |
C71—C7—C3 | 116.33 (13) | C15—C24—H24 | 121.1 |
C8—C7—C3 | 103.35 (13) | C23—C24—H24 | 121.1 |
C71—C7—H7 | 107.1 | C75—C76—C71 | 122.07 (18) |
C8—C7—H7 | 107.1 | C75—C76—H76 | 119.0 |
C3—C7—H7 | 107.1 | C71—C76—H76 | 119.0 |
N1—C13—C17 | 109.97 (13) | C19—C20—C21 | 120.86 (17) |
N1—C13—C14 | 114.26 (14) | C19—C20—H20 | 119.6 |
C17—C13—C14 | 101.29 (13) | C21—C20—H20 | 119.6 |
N1—C13—C3 | 103.18 (12) | C22—C23—C24 | 122.75 (18) |
C17—C13—C3 | 116.83 (13) | C22—C23—H23 | 118.6 |
C14—C13—C3 | 111.79 (13) | C24—C23—H23 | 118.6 |
C2—N2—C1 | 112.59 (14) | N1—C12—C11 | 109.27 (17) |
C2—N2—C6 | 110.89 (14) | N1—C12—H12A | 109.8 |
C1—N2—C6 | 111.54 (15) | C11—C12—H12A | 109.8 |
O1—C4—C5 | 121.23 (16) | N1—C12—H12B | 109.8 |
O1—C4—C3 | 121.60 (16) | C11—C12—H12B | 109.8 |
C5—C4—C3 | 117.17 (15) | H12A—C12—H12B | 108.3 |
N2—C6—C5 | 112.01 (15) | C17—C18—C19 | 118.81 (17) |
N2—C6—H6A | 109.2 | C17—C18—H18 | 120.6 |
C5—C6—H6A | 109.2 | C19—C18—H18 | 120.6 |
N2—C6—H6B | 109.2 | C74—C73—C72 | 119.55 (17) |
C5—C6—H6B | 109.2 | C74—C73—H73 | 120.2 |
H6A—C6—H6B | 107.9 | C72—C73—H73 | 120.2 |
C72—C71—C76 | 117.25 (16) | C74—C75—C76 | 118.84 (18) |
C72—C71—C7 | 120.31 (16) | C74—C75—H75 | 120.6 |
C76—C71—C7 | 122.42 (16) | C76—C75—H75 | 120.6 |
C5—C51—C52 | 130.55 (18) | C56—C55—C54 | 121.0 (2) |
C5—C51—H51 | 114.7 | C56—C55—Cl2 | 119.89 (18) |
C52—C51—H51 | 114.7 | C54—C55—Cl2 | 119.13 (18) |
C16—C21—C20 | 115.82 (17) | C55—C54—C53 | 119.1 (2) |
C16—C21—C22 | 115.27 (18) | C55—C54—H54 | 120.5 |
C20—C21—C22 | 128.90 (18) | C53—C54—H54 | 120.5 |
C2—C3—C4 | 107.26 (14) | C8—C9—C10 | 110.89 (17) |
C2—C3—C7 | 112.44 (13) | C8—C9—H9A | 109.5 |
C4—C3—C7 | 113.04 (14) | C10—C9—H9A | 109.5 |
C2—C3—C13 | 111.31 (13) | C8—C9—H9B | 109.5 |
C4—C3—C13 | 109.70 (13) | C10—C9—H9B | 109.5 |
C7—C3—C13 | 103.12 (13) | H9A—C9—H9B | 108.0 |
C18—C17—C16 | 119.00 (16) | C23—C22—C21 | 120.88 (19) |
C18—C17—C13 | 131.08 (15) | C23—C22—H22 | 119.6 |
C16—C17—C13 | 109.81 (14) | C21—C22—H22 | 119.6 |
O2—C14—C15 | 127.07 (17) | N2—C1—H1A | 109.5 |
O2—C14—C13 | 124.48 (16) | N2—C1—H1B | 109.5 |
C15—C14—C13 | 107.78 (14) | H1A—C1—H1B | 109.5 |
C75—C74—C73 | 120.88 (16) | N2—C1—H1C | 109.5 |
C75—C74—Cl1 | 119.19 (15) | H1A—C1—H1C | 109.5 |
C73—C74—Cl1 | 119.90 (15) | H1B—C1—H1C | 109.5 |
N1—C8—C9 | 110.34 (15) | C54—C53—C52 | 121.8 (2) |
N1—C8—C7 | 100.73 (13) | C54—C53—H53 | 119.1 |
C9—C8—C7 | 115.74 (16) | C52—C53—H53 | 119.1 |
N1—C8—H8 | 109.9 | C56—C57—C52 | 121.09 (19) |
C9—C8—H8 | 109.9 | C56—C57—H57 | 119.5 |
C7—C8—H8 | 109.9 | C52—C57—H57 | 119.5 |
C24—C15—C16 | 119.59 (17) | C9—C10—C11 | 110.04 (18) |
C24—C15—C14 | 132.85 (18) | C9—C10—H10A | 109.7 |
C16—C15—C14 | 107.46 (15) | C11—C10—H10A | 109.7 |
C73—C72—C71 | 121.41 (17) | C9—C10—H10B | 109.7 |
C73—C72—H72 | 119.3 | C11—C10—H10B | 109.7 |
C71—C72—H72 | 119.3 | H10A—C10—H10B | 108.2 |
N2—C2—C3 | 108.72 (13) | C55—C56—C57 | 119.6 (2) |
N2—C2—H2A | 109.9 | C55—C56—H56 | 120.2 |
C3—C2—H2A | 109.9 | C57—C56—H56 | 120.2 |
N2—C2—H2B | 109.9 | C10—C11—C12 | 110.47 (18) |
C3—C2—H2B | 109.9 | C10—C11—H11A | 109.6 |
H2A—C2—H2B | 108.3 | C12—C11—H11A | 109.6 |
C51—C5—C6 | 124.03 (17) | C10—C11—H11B | 109.6 |
C51—C5—C4 | 116.83 (16) | C12—C11—H11B | 109.6 |
C6—C5—C4 | 119.11 (15) | H11A—C11—H11B | 108.1 |
C8—N1—C13—C17 | 154.02 (14) | C21—C16—C15—C24 | −2.6 (3) |
C12—N1—C13—C17 | −74.14 (19) | C17—C16—C15—C14 | −3.0 (2) |
C8—N1—C13—C14 | −92.89 (16) | C21—C16—C15—C14 | 174.40 (16) |
C12—N1—C13—C14 | 39.0 (2) | O2—C14—C15—C24 | 12.2 (3) |
C8—N1—C13—C3 | 28.69 (17) | C13—C14—C15—C24 | −176.95 (19) |
C12—N1—C13—C3 | 160.53 (15) | O2—C14—C15—C16 | −164.31 (18) |
C2—N2—C6—C5 | 52.69 (19) | C13—C14—C15—C16 | 6.59 (18) |
C1—N2—C6—C5 | 179.04 (16) | C76—C71—C72—C73 | −0.2 (3) |
C8—C7—C71—C72 | 146.51 (17) | C7—C71—C72—C73 | −178.48 (16) |
C3—C7—C71—C72 | −92.2 (2) | C1—N2—C2—C3 | 161.35 (16) |
C8—C7—C71—C76 | −31.7 (2) | C6—N2—C2—C3 | −72.88 (18) |
C3—C7—C71—C76 | 89.6 (2) | C4—C3—C2—N2 | 61.91 (17) |
C15—C16—C21—C20 | −175.04 (17) | C7—C3—C2—N2 | −173.22 (14) |
C17—C16—C21—C20 | 2.1 (3) | C13—C3—C2—N2 | −58.09 (18) |
C15—C16—C21—C22 | 3.5 (3) | C52—C51—C5—C6 | 2.4 (3) |
C17—C16—C21—C22 | −179.40 (16) | C52—C51—C5—C4 | −179.48 (18) |
O1—C4—C3—C2 | 143.79 (16) | N2—C6—C5—C51 | 150.50 (18) |
C5—C4—C3—C2 | −37.17 (19) | N2—C6—C5—C4 | −27.6 (2) |
O1—C4—C3—C7 | 19.3 (2) | O1—C4—C5—C51 | 22.6 (2) |
C5—C4—C3—C7 | −161.68 (14) | C3—C4—C5—C51 | −156.42 (16) |
O1—C4—C3—C13 | −95.18 (18) | O1—C4—C5—C6 | −159.19 (17) |
C5—C4—C3—C13 | 83.86 (17) | C3—C4—C5—C6 | 21.8 (2) |
C71—C7—C3—C2 | −33.4 (2) | C5—C51—C52—C57 | 31.6 (3) |
C8—C7—C3—C2 | 94.06 (16) | C5—C51—C52—C53 | −151.9 (2) |
C71—C7—C3—C4 | 88.23 (18) | C16—C15—C24—C23 | −0.4 (3) |
C8—C7—C3—C4 | −144.31 (14) | C14—C15—C24—C23 | −176.51 (19) |
C71—C7—C3—C13 | −153.41 (14) | C72—C71—C76—C75 | −0.7 (3) |
C8—C7—C3—C13 | −25.94 (16) | C7—C71—C76—C75 | 177.56 (18) |
N1—C13—C3—C2 | −121.20 (14) | C18—C19—C20—C21 | −1.0 (3) |
C17—C13—C3—C2 | 118.03 (16) | C16—C21—C20—C19 | −0.1 (3) |
C14—C13—C3—C2 | 2.04 (19) | C22—C21—C20—C19 | −178.4 (2) |
N1—C13—C3—C4 | 120.25 (14) | C15—C24—C23—C22 | 2.4 (3) |
C17—C13—C3—C4 | −0.5 (2) | C8—N1—C12—C11 | −58.0 (2) |
C14—C13—C3—C4 | −116.51 (15) | C13—N1—C12—C11 | 172.85 (16) |
N1—C13—C3—C7 | −0.43 (16) | C16—C17—C18—C19 | 1.7 (3) |
C17—C13—C3—C7 | −121.19 (15) | C13—C17—C18—C19 | 177.35 (17) |
C14—C13—C3—C7 | 122.81 (14) | C20—C19—C18—C17 | 0.2 (3) |
C15—C16—C17—C18 | 174.47 (16) | C75—C74—C73—C72 | −0.9 (3) |
C21—C16—C17—C18 | −2.9 (3) | Cl1—C74—C73—C72 | 177.12 (15) |
C15—C16—C17—C13 | −2.0 (2) | C71—C72—C73—C74 | 1.0 (3) |
C21—C16—C17—C13 | −179.45 (15) | C73—C74—C75—C76 | 0.0 (3) |
N1—C13—C17—C18 | −49.0 (2) | Cl1—C74—C75—C76 | −177.98 (15) |
C14—C13—C17—C18 | −170.25 (18) | C71—C76—C75—C74 | 0.8 (3) |
C3—C13—C17—C18 | 68.1 (2) | C56—C55—C54—C53 | −0.9 (4) |
N1—C13—C17—C16 | 126.93 (15) | Cl2—C55—C54—C53 | 178.73 (18) |
C14—C13—C17—C16 | 5.71 (17) | N1—C8—C9—C10 | −55.0 (2) |
C3—C13—C17—C16 | −115.96 (16) | C7—C8—C9—C10 | −168.55 (17) |
N1—C13—C14—O2 | 45.7 (2) | C24—C23—C22—C21 | −1.5 (3) |
C17—C13—C14—O2 | 163.85 (17) | C16—C21—C22—C23 | −1.4 (3) |
C3—C13—C14—O2 | −71.0 (2) | C20—C21—C22—C23 | 176.9 (2) |
N1—C13—C14—C15 | −125.51 (15) | C55—C54—C53—C52 | 1.3 (3) |
C17—C13—C14—C15 | −7.35 (17) | C57—C52—C53—C54 | −1.0 (3) |
C3—C13—C14—C15 | 117.78 (15) | C51—C52—C53—C54 | −177.8 (2) |
C12—N1—C8—C9 | 57.7 (2) | C53—C52—C57—C56 | 0.2 (3) |
C13—N1—C8—C9 | −168.56 (15) | C51—C52—C57—C56 | 176.79 (18) |
C12—N1—C8—C7 | −179.52 (15) | C8—C9—C10—C11 | 55.3 (3) |
C13—N1—C8—C7 | −45.76 (17) | C54—C55—C56—C57 | 0.1 (3) |
C71—C7—C8—N1 | 171.17 (14) | Cl2—C55—C56—C57 | −179.47 (16) |
C3—C7—C8—N1 | 43.08 (16) | C52—C57—C56—C55 | 0.2 (3) |
C71—C7—C8—C9 | −69.9 (2) | C9—C10—C11—C12 | −56.0 (3) |
C3—C7—C8—C9 | 162.04 (15) | N1—C12—C11—C10 | 56.2 (3) |
C17—C16—C15—C24 | 179.99 (16) |
Cg1 is the centroid of the C52–C57 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1 | 0.98 | 2.38 | 2.826 (2) | 107 |
C2—H2A···O2 | 0.97 | 2.45 | 2.951 (2) | 112 |
C75—H75···Cg1i | 0.93 | 2.88 | 3.669 (2) | 144 |
Symmetry code: (i) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C37H32Cl2N2O2 |
Mr | 607.55 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 14.1346 (5), 15.2184 (6), 14.5603 (6) |
β (°) | 102.337 (1) |
V (Å3) | 3059.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.21 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Bruker Kappa APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.967, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32144, 7321, 4492 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.113, 1.01 |
No. of reflections | 7321 |
No. of parameters | 389 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.38 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Cg1 is the centroid of the C52–C57 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C75—H75···Cg1i | 0.93 | 2.88 | 3.669 (2) | 144 |
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
Gundersen, L.-L., Charnock, C., Negussie, A. H., Rise, F. & Teklu, S. (2007). Eur. J. Pharm. Sci. 30, 26–35. Web of Science CrossRef PubMed 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
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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.
Indolizines are electron-rich heterocycles with very low oxidation potentials. Functionalised indolizines are common substructures found in biologically important natural products and synthetic pharmaceuticals. Due to the various biological functions associated with this skeleton, it has been frequently employed as a key scaffold in the drug industry (Gundersen et al., 2007).
In the title compound (Fig.1), the pyridinone ring adopts twisted half chair conformation with atoms N2 and C3 deviating by 0.6030 (1) Å and 0.4814 (1) Å respectively from the least squares planes defined by other atoms (C2/C4/C5/C6). Within the octahydroindolizine, the six membered piperidine ring adopts a chair conformation as evident from the puckering parameters Q = 0.567 (2) Å, θ = 180 (2)° and Φ = 50 (8)° (Cremer & Pople, 1975). The dihedral angle between the two chlorobenzene rings is 84.03 (1)°, and these rings (C71—C76) and (C52—C57) form angles of 80.91 (1) and 32.50 (1)°, respectively, with the plane defined by atoms (C2/C4/C5/C6) of pyridinone ring. Each of the carbonyl bond lengths, i.e C4=O1 and C14=O2, is 1.214 (2) Å, and each of these atoms participates in two intramolecular C—H···O contacts, with the closest of these listed in Table 1. The C8—N1 bond length (1.454 (2) Å) is comparable with the Csp2—Nsp2 distance found in the similar structures (Sussman & Wodak, 1973; Wodak, 1975).
A weak intermolecular C—H···π interaction, viz. C75—H75···Cg1 (Cg1 is the centroid of the ring C52—C57; symmetry code is given in Table 1) is observed. These lead to supramolecular chains along [101] that assemble in the ac plane. Connections between layers are of the type Cl···Cl (Cl1···Cl1i = 3.4065 (8) Å: symmetry code: 1 - x, 1 - y, 2 - z).