organic compounds
Methyl 3′-benzyl-4′-(2,4-dichlorophenyl)-1′-methyl-2-oxospiro[indoline-3,2′-pyrrolidine]-3′-carboxylate
aDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and bDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
*Correspondence e-mail: ksethusankar@yahoo.co.in
In the title compound, C27H24Cl2N2O3, the indole ring system is essentially planar, with a maximum deviation of 0.082 (2) Å for the carbonyl C atom. It makes a dihedral angle of 88.53 (6)° with the mean plane of the 4-methylpyrrolidine ring, which adopts an with the N atom at the flap position. The molecular structure is stabilized by intramolecular C—H⋯O hydrogen bonds, which generate S(6) and S(7) ring motifs, and an intramolecular π–π interaction involving the benzyl and dichloro-substituted benzene rings [centroid–centroid distance = 3.6291 (11) Å]. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming C(7) chains running parallel to [10-1].
CCDC reference: 888482
Related literature
For the biological activity of spiro-oxindole derivatives, see: Hilton et al. (2000). For a related see: Karthikeyan et al. (2014). For puckering parameters, see: Cremer & Pople (1975). For graph-set motifs, see: Bernstein et al. (1995). For bond-length distortions in small rings, see: Allen (1981).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
CCDC reference: 888482
10.1107/S1600536814003523/su2699sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814003523/su2699Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814003523/su2699Isup3.cml
A mixture of (E)-methyl 2-benzyl-3-(2,4-dichlorophenyl)acrylate (2 mmol), isatin (2 mmol) and sarcosine (2 mmol) in acetonitrile (8 ml) was refluxed for 12 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated. The resulting crude mass was diluted with water (10 ml) and extracted with ethyl acetate (3 × 10 ml). The combined organic layers were washed with brine (2 × 10 ml) and dried over anhydrous Na2SO4. The organic layer was concentrated and the residue purified by
on silica gel (Acme 100–200 mesh), using ethyl acetate:hexanes (2:8) to afford the title compound as a colourless solid in (65%) yield. Block-like colourless crystals were obtained by slow evaporation of a solution in CHCl3.The H atoms could all be located in difference electron-density maps. In the final cycles of
they were treated as riding atoms and their distances were geometrically constrained: N-H = 0.86 Å, C—H = 0.93 - 0.98 Å with Uiso(H) = 1.5 Ueq(C– methyl) and = 1.2Ueq(N/C) for other H atoms.Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C27H24Cl2N2O3 | F(000) = 1032 |
Mr = 495.38 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2yn | Cell parameters from 6466 reflections |
a = 12.7051 (5) Å | θ = 2.1–29.3° |
b = 14.1724 (6) Å | µ = 0.31 mm−1 |
c = 14.0322 (6) Å | T = 293 K |
β = 109.424 (2)° | Block, colorless |
V = 2382.85 (17) Å3 | 0.30 × 0.28 × 0.25 mm |
Z = 4 |
Bruker Kappa APEXII CCD diffractometer | 4356 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 29.3°, θmin = 2.1° |
ω scans | h = −16→17 |
27865 measured reflections | k = −19→13 |
6466 independent reflections | l = −18→19 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0537P)2 + 0.8129P] where P = (Fo2 + 2Fc2)/3 |
6466 reflections | (Δ/σ)max < 0.001 |
309 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
C27H24Cl2N2O3 | V = 2382.85 (17) Å3 |
Mr = 495.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.7051 (5) Å | µ = 0.31 mm−1 |
b = 14.1724 (6) Å | T = 293 K |
c = 14.0322 (6) Å | 0.30 × 0.28 × 0.25 mm |
β = 109.424 (2)° |
Bruker Kappa APEXII CCD diffractometer | 4356 reflections with I > 2σ(I) |
27865 measured reflections | Rint = 0.028 |
6466 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.41 e Å−3 |
6466 reflections | Δρmin = −0.49 e Å−3 |
309 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 | 0.58285 (14) | 0.31080 (12) | 0.42423 (13) | 0.0422 (4) | |
C2 | 0.66005 (15) | 0.33021 (13) | 0.37693 (14) | 0.0483 (4) | |
H2 | 0.7301 | 0.3019 | 0.3985 | 0.058* | |
C3 | 0.63062 (15) | 0.39240 (13) | 0.29724 (15) | 0.0484 (4) | |
C4 | 0.52940 (16) | 0.43704 (13) | 0.26718 (15) | 0.0507 (5) | |
H4 | 0.5118 | 0.4809 | 0.2149 | 0.061* | |
C5 | 0.45350 (15) | 0.41603 (13) | 0.31561 (14) | 0.0459 (4) | |
H5 | 0.3848 | 0.4465 | 0.2951 | 0.055* | |
C6 | 0.47685 (13) | 0.35069 (12) | 0.39402 (12) | 0.0393 (4) | |
C7 | 0.39119 (14) | 0.32433 (12) | 0.44254 (12) | 0.0389 (4) | |
H7 | 0.4320 | 0.2961 | 0.5082 | 0.047* | |
C8 | 0.32681 (16) | 0.40830 (13) | 0.46311 (15) | 0.0502 (4) | |
H8A | 0.3672 | 0.4374 | 0.5275 | 0.060* | |
H8B | 0.3137 | 0.4553 | 0.4102 | 0.060* | |
C9 | 0.18556 (13) | 0.30092 (11) | 0.38043 (11) | 0.0346 (3) | |
C10 | 0.12965 (15) | 0.34886 (13) | 0.27525 (12) | 0.0426 (4) | |
C11 | 0.00156 (14) | 0.24664 (13) | 0.29794 (14) | 0.0449 (4) | |
C12 | −0.09784 (16) | 0.19937 (16) | 0.28444 (19) | 0.0649 (6) | |
H12 | −0.1569 | 0.2036 | 0.2239 | 0.078* | |
C13 | −0.10630 (18) | 0.14611 (16) | 0.3634 (2) | 0.0670 (6) | |
H13 | −0.1722 | 0.1139 | 0.3562 | 0.080* | |
C14 | −0.01904 (18) | 0.13971 (14) | 0.45262 (18) | 0.0581 (5) | |
H14 | −0.0266 | 0.1033 | 0.5051 | 0.070* | |
C15 | 0.08044 (15) | 0.18687 (13) | 0.46545 (14) | 0.0446 (4) | |
H15 | 0.1391 | 0.1829 | 0.5263 | 0.054* | |
C16 | 0.09119 (13) | 0.23953 (12) | 0.38709 (12) | 0.0373 (4) | |
C17 | 0.29931 (12) | 0.25062 (11) | 0.38356 (11) | 0.0311 (3) | |
C18 | 0.29733 (13) | 0.22452 (11) | 0.27577 (11) | 0.0339 (3) | |
H18A | 0.2346 | 0.1824 | 0.2471 | 0.041* | |
H18B | 0.2812 | 0.2819 | 0.2358 | 0.041* | |
C19 | 0.39826 (12) | 0.17915 (11) | 0.25989 (11) | 0.0334 (3) | |
C20 | 0.42743 (15) | 0.21109 (13) | 0.17845 (13) | 0.0447 (4) | |
H20 | 0.3863 | 0.2595 | 0.1384 | 0.054* | |
C21 | 0.51556 (17) | 0.17291 (15) | 0.15552 (16) | 0.0561 (5) | |
H21 | 0.5334 | 0.1958 | 0.1007 | 0.067* | |
C22 | 0.57727 (16) | 0.10121 (14) | 0.21310 (15) | 0.0522 (5) | |
H22 | 0.6376 | 0.0759 | 0.1983 | 0.063* | |
C23 | 0.54893 (15) | 0.06731 (13) | 0.29259 (14) | 0.0464 (4) | |
H23 | 0.5897 | 0.0180 | 0.3313 | 0.056* | |
C24 | 0.46040 (14) | 0.10554 (12) | 0.31595 (12) | 0.0401 (4) | |
H24 | 0.4423 | 0.0814 | 0.3702 | 0.048* | |
C25 | 0.30887 (12) | 0.16134 (11) | 0.44713 (11) | 0.0331 (3) | |
C26 | 0.25651 (17) | 0.00191 (13) | 0.44542 (15) | 0.0532 (5) | |
H26A | 0.3325 | −0.0180 | 0.4765 | 0.080* | |
H26B | 0.2161 | −0.0455 | 0.3986 | 0.080* | |
H26C | 0.2226 | 0.0109 | 0.4965 | 0.080* | |
C27 | 0.13946 (19) | 0.43922 (15) | 0.46547 (17) | 0.0609 (5) | |
H27A | 0.1663 | 0.4751 | 0.5269 | 0.091* | |
H27B | 0.0706 | 0.4089 | 0.4616 | 0.091* | |
H27C | 0.1273 | 0.4806 | 0.4086 | 0.091* | |
N1 | 0.22212 (12) | 0.36773 (10) | 0.46454 (10) | 0.0426 (3) | |
N2 | 0.02779 (13) | 0.31006 (12) | 0.23303 (11) | 0.0521 (4) | |
H2A | −0.0160 | 0.3229 | 0.1730 | 0.063* | |
O1 | 0.16988 (12) | 0.41046 (10) | 0.23798 (10) | 0.0562 (4) | |
O2 | 0.35713 (10) | 0.15537 (9) | 0.53672 (8) | 0.0471 (3) | |
O3 | 0.25399 (9) | 0.08941 (8) | 0.39242 (8) | 0.0379 (3) | |
Cl1 | 0.62311 (4) | 0.23046 (4) | 0.52348 (4) | 0.06078 (16) | |
Cl2 | 0.72403 (5) | 0.41173 (4) | 0.23263 (5) | 0.07259 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0388 (9) | 0.0436 (9) | 0.0367 (9) | −0.0069 (7) | 0.0025 (7) | 0.0008 (7) |
C2 | 0.0367 (9) | 0.0496 (11) | 0.0534 (11) | −0.0066 (7) | 0.0082 (8) | −0.0034 (8) |
C3 | 0.0468 (10) | 0.0445 (10) | 0.0570 (11) | −0.0149 (8) | 0.0214 (9) | −0.0047 (8) |
C4 | 0.0542 (11) | 0.0432 (10) | 0.0550 (11) | −0.0088 (8) | 0.0185 (9) | 0.0090 (8) |
C5 | 0.0411 (9) | 0.0446 (10) | 0.0488 (10) | −0.0032 (7) | 0.0106 (8) | 0.0072 (8) |
C6 | 0.0371 (8) | 0.0400 (9) | 0.0355 (8) | −0.0079 (7) | 0.0052 (7) | 0.0000 (7) |
C7 | 0.0380 (8) | 0.0435 (9) | 0.0300 (8) | −0.0073 (7) | 0.0044 (6) | 0.0007 (7) |
C8 | 0.0594 (11) | 0.0451 (10) | 0.0478 (11) | −0.0102 (8) | 0.0201 (9) | −0.0114 (8) |
C9 | 0.0356 (8) | 0.0392 (8) | 0.0281 (8) | 0.0044 (6) | 0.0094 (6) | 0.0030 (6) |
C10 | 0.0469 (10) | 0.0471 (10) | 0.0342 (9) | 0.0186 (8) | 0.0141 (7) | 0.0067 (7) |
C11 | 0.0382 (9) | 0.0475 (10) | 0.0444 (10) | 0.0092 (7) | 0.0076 (8) | −0.0071 (8) |
C12 | 0.0387 (10) | 0.0653 (14) | 0.0781 (16) | 0.0025 (9) | 0.0025 (10) | −0.0212 (12) |
C13 | 0.0462 (11) | 0.0567 (13) | 0.1007 (19) | −0.0084 (9) | 0.0278 (12) | −0.0159 (13) |
C14 | 0.0586 (12) | 0.0504 (11) | 0.0786 (15) | −0.0027 (9) | 0.0406 (12) | −0.0035 (10) |
C15 | 0.0450 (9) | 0.0482 (10) | 0.0463 (10) | 0.0033 (8) | 0.0229 (8) | −0.0004 (8) |
C16 | 0.0338 (8) | 0.0415 (9) | 0.0371 (9) | 0.0057 (6) | 0.0125 (7) | −0.0040 (7) |
C17 | 0.0290 (7) | 0.0365 (8) | 0.0245 (7) | 0.0008 (6) | 0.0043 (6) | 0.0029 (6) |
C18 | 0.0326 (8) | 0.0417 (9) | 0.0248 (7) | 0.0037 (6) | 0.0060 (6) | 0.0039 (6) |
C19 | 0.0315 (7) | 0.0379 (8) | 0.0286 (7) | −0.0015 (6) | 0.0071 (6) | −0.0019 (6) |
C20 | 0.0495 (10) | 0.0466 (10) | 0.0420 (10) | 0.0084 (8) | 0.0205 (8) | 0.0100 (8) |
C21 | 0.0635 (12) | 0.0614 (12) | 0.0562 (12) | 0.0072 (10) | 0.0369 (10) | 0.0125 (10) |
C22 | 0.0440 (10) | 0.0588 (12) | 0.0603 (12) | 0.0069 (8) | 0.0263 (9) | −0.0008 (9) |
C23 | 0.0416 (9) | 0.0478 (10) | 0.0469 (10) | 0.0102 (8) | 0.0110 (8) | 0.0038 (8) |
C24 | 0.0414 (9) | 0.0454 (10) | 0.0338 (8) | 0.0041 (7) | 0.0128 (7) | 0.0053 (7) |
C25 | 0.0282 (7) | 0.0409 (8) | 0.0272 (7) | 0.0022 (6) | 0.0053 (6) | 0.0019 (6) |
C26 | 0.0685 (13) | 0.0385 (10) | 0.0508 (11) | −0.0036 (9) | 0.0175 (10) | 0.0076 (8) |
C27 | 0.0754 (14) | 0.0522 (12) | 0.0647 (13) | 0.0093 (10) | 0.0362 (11) | −0.0085 (10) |
N1 | 0.0498 (8) | 0.0424 (8) | 0.0365 (8) | 0.0002 (6) | 0.0156 (6) | −0.0062 (6) |
N2 | 0.0453 (9) | 0.0654 (10) | 0.0348 (8) | 0.0157 (7) | −0.0012 (6) | 0.0029 (7) |
O1 | 0.0649 (9) | 0.0567 (8) | 0.0516 (8) | 0.0211 (7) | 0.0253 (7) | 0.0221 (6) |
O2 | 0.0499 (7) | 0.0546 (7) | 0.0272 (6) | −0.0063 (6) | 0.0000 (5) | 0.0084 (5) |
O3 | 0.0422 (6) | 0.0362 (6) | 0.0320 (6) | −0.0011 (5) | 0.0079 (5) | 0.0016 (4) |
Cl1 | 0.0510 (3) | 0.0749 (4) | 0.0453 (3) | 0.0069 (2) | 0.0010 (2) | 0.0180 (2) |
Cl2 | 0.0699 (4) | 0.0693 (4) | 0.0948 (5) | −0.0121 (3) | 0.0490 (3) | 0.0052 (3) |
C1—C2 | 1.383 (3) | C14—C15 | 1.388 (3) |
C1—C6 | 1.390 (2) | C14—H14 | 0.9300 |
C1—Cl1 | 1.7389 (18) | C15—C16 | 1.373 (2) |
C2—C3 | 1.374 (3) | C15—H15 | 0.9300 |
C2—H2 | 0.9300 | C17—C25 | 1.530 (2) |
C3—C4 | 1.368 (3) | C17—C18 | 1.549 (2) |
C3—Cl2 | 1.7381 (19) | C18—C19 | 1.516 (2) |
C4—C5 | 1.384 (2) | C18—H18A | 0.9700 |
C4—H4 | 0.9300 | C18—H18B | 0.9700 |
C5—C6 | 1.393 (2) | C19—C24 | 1.385 (2) |
C5—H5 | 0.9300 | C19—C20 | 1.389 (2) |
C6—C7 | 1.510 (2) | C20—C21 | 1.375 (3) |
C7—C8 | 1.525 (3) | C20—H20 | 0.9300 |
C7—C17 | 1.580 (2) | C21—C22 | 1.371 (3) |
C7—H7 | 0.9800 | C21—H21 | 0.9300 |
C8—N1 | 1.455 (2) | C22—C23 | 1.368 (3) |
C8—H8A | 0.9700 | C22—H22 | 0.9300 |
C8—H8B | 0.9700 | C23—C24 | 1.382 (2) |
C9—N1 | 1.463 (2) | C23—H23 | 0.9300 |
C9—C16 | 1.509 (2) | C24—H24 | 0.9300 |
C9—C10 | 1.564 (2) | C25—O2 | 1.2045 (18) |
C9—C17 | 1.599 (2) | C25—O3 | 1.3262 (19) |
C10—O1 | 1.214 (2) | C26—O3 | 1.441 (2) |
C10—N2 | 1.348 (2) | C26—H26A | 0.9600 |
C11—C12 | 1.386 (3) | C26—H26B | 0.9600 |
C11—C16 | 1.387 (2) | C26—H26C | 0.9600 |
C11—N2 | 1.397 (3) | C27—N1 | 1.462 (2) |
C12—C13 | 1.374 (3) | C27—H27A | 0.9600 |
C12—H12 | 0.9300 | C27—H27B | 0.9600 |
C13—C14 | 1.372 (3) | C27—H27C | 0.9600 |
C13—H13 | 0.9300 | N2—H2A | 0.8600 |
C2—C1—C6 | 122.86 (16) | C15—C16—C9 | 130.97 (15) |
C2—C1—Cl1 | 116.62 (14) | C11—C16—C9 | 109.45 (15) |
C6—C1—Cl1 | 120.50 (13) | C25—C17—C18 | 110.14 (12) |
C3—C2—C1 | 118.27 (17) | C25—C17—C7 | 109.87 (12) |
C3—C2—H2 | 120.9 | C18—C17—C7 | 116.02 (13) |
C1—C2—H2 | 120.9 | C25—C17—C9 | 106.29 (12) |
C4—C3—C2 | 121.40 (17) | C18—C17—C9 | 111.02 (11) |
C4—C3—Cl2 | 120.08 (15) | C7—C17—C9 | 102.90 (12) |
C2—C3—Cl2 | 118.51 (15) | C19—C18—C17 | 120.33 (12) |
C3—C4—C5 | 119.09 (17) | C19—C18—H18A | 107.2 |
C3—C4—H4 | 120.5 | C17—C18—H18A | 107.2 |
C5—C4—H4 | 120.5 | C19—C18—H18B | 107.2 |
C4—C5—C6 | 122.06 (17) | C17—C18—H18B | 107.2 |
C4—C5—H5 | 119.0 | H18A—C18—H18B | 106.9 |
C6—C5—H5 | 119.0 | C24—C19—C20 | 117.08 (15) |
C1—C6—C5 | 116.20 (16) | C24—C19—C18 | 125.91 (14) |
C1—C6—C7 | 122.15 (15) | C20—C19—C18 | 116.92 (14) |
C5—C6—C7 | 121.65 (15) | C21—C20—C19 | 121.67 (17) |
C6—C7—C8 | 113.87 (14) | C21—C20—H20 | 119.2 |
C6—C7—C17 | 116.42 (13) | C19—C20—H20 | 119.2 |
C8—C7—C17 | 105.41 (13) | C22—C21—C20 | 120.30 (17) |
C6—C7—H7 | 106.9 | C22—C21—H21 | 119.8 |
C8—C7—H7 | 106.9 | C20—C21—H21 | 119.8 |
C17—C7—H7 | 106.9 | C23—C22—C21 | 119.14 (17) |
N1—C8—C7 | 104.15 (14) | C23—C22—H22 | 120.4 |
N1—C8—H8A | 110.9 | C21—C22—H22 | 120.4 |
C7—C8—H8A | 110.9 | C22—C23—C24 | 120.74 (17) |
N1—C8—H8B | 110.9 | C22—C23—H23 | 119.6 |
C7—C8—H8B | 110.9 | C24—C23—H23 | 119.6 |
H8A—C8—H8B | 108.9 | C23—C24—C19 | 121.04 (16) |
N1—C9—C16 | 111.63 (12) | C23—C24—H24 | 119.5 |
N1—C9—C10 | 113.75 (13) | C19—C24—H24 | 119.5 |
C16—C9—C10 | 100.84 (13) | O2—C25—O3 | 122.50 (14) |
N1—C9—C17 | 102.99 (12) | O2—C25—C17 | 125.52 (14) |
C16—C9—C17 | 118.08 (13) | O3—C25—C17 | 111.95 (12) |
C10—C9—C17 | 110.01 (12) | O3—C26—H26A | 109.5 |
O1—C10—N2 | 125.73 (16) | O3—C26—H26B | 109.5 |
O1—C10—C9 | 126.47 (17) | H26A—C26—H26B | 109.5 |
N2—C10—C9 | 107.80 (15) | O3—C26—H26C | 109.5 |
C12—C11—C16 | 121.71 (19) | H26A—C26—H26C | 109.5 |
C12—C11—N2 | 128.77 (18) | H26B—C26—H26C | 109.5 |
C16—C11—N2 | 109.43 (16) | N1—C27—H27A | 109.5 |
C13—C12—C11 | 117.9 (2) | N1—C27—H27B | 109.5 |
C13—C12—H12 | 121.1 | H27A—C27—H27B | 109.5 |
C11—C12—H12 | 121.1 | N1—C27—H27C | 109.5 |
C14—C13—C12 | 121.1 (2) | H27A—C27—H27C | 109.5 |
C14—C13—H13 | 119.5 | H27B—C27—H27C | 109.5 |
C12—C13—H13 | 119.5 | C8—N1—C27 | 112.88 (15) |
C13—C14—C15 | 120.8 (2) | C8—N1—C9 | 106.92 (13) |
C13—C14—H14 | 119.6 | C27—N1—C9 | 114.79 (14) |
C15—C14—H14 | 119.6 | C10—N2—C11 | 112.22 (14) |
C16—C15—C14 | 119.13 (18) | C10—N2—H2A | 123.9 |
C16—C15—H15 | 120.4 | C11—N2—H2A | 123.9 |
C14—C15—H15 | 120.4 | C25—O3—C26 | 116.46 (13) |
C15—C16—C11 | 119.43 (16) | ||
C6—C1—C2—C3 | 0.7 (3) | C8—C7—C17—C18 | 118.92 (15) |
Cl1—C1—C2—C3 | 179.12 (14) | C6—C7—C17—C9 | −129.76 (14) |
C1—C2—C3—C4 | 2.4 (3) | C8—C7—C17—C9 | −2.49 (16) |
C1—C2—C3—Cl2 | −176.21 (14) | N1—C9—C17—C25 | 93.64 (13) |
C2—C3—C4—C5 | −2.7 (3) | C16—C9—C17—C25 | −29.85 (17) |
Cl2—C3—C4—C5 | 175.91 (15) | C10—C9—C17—C25 | −144.76 (13) |
C3—C4—C5—C6 | −0.1 (3) | N1—C9—C17—C18 | −146.58 (13) |
C2—C1—C6—C5 | −3.2 (3) | C16—C9—C17—C18 | 89.92 (16) |
Cl1—C1—C6—C5 | 178.40 (13) | C10—C9—C17—C18 | −24.99 (18) |
C2—C1—C6—C7 | 176.31 (16) | N1—C9—C17—C7 | −21.83 (14) |
Cl1—C1—C6—C7 | −2.1 (2) | C16—C9—C17—C7 | −145.33 (13) |
C4—C5—C6—C1 | 2.9 (3) | C10—C9—C17—C7 | 99.76 (14) |
C4—C5—C6—C7 | −176.61 (17) | C25—C17—C18—C19 | −64.72 (18) |
C1—C6—C7—C8 | 137.44 (17) | C7—C17—C18—C19 | 60.85 (19) |
C5—C6—C7—C8 | −43.1 (2) | C9—C17—C18—C19 | 177.83 (13) |
C1—C6—C7—C17 | −99.58 (18) | C17—C18—C19—C24 | 45.3 (2) |
C5—C6—C7—C17 | 79.9 (2) | C17—C18—C19—C20 | −138.30 (16) |
C6—C7—C8—N1 | 155.06 (14) | C24—C19—C20—C21 | −1.4 (3) |
C17—C7—C8—N1 | 26.25 (17) | C18—C19—C20—C21 | −178.13 (17) |
N1—C9—C10—O1 | 54.9 (2) | C19—C20—C21—C22 | 0.2 (3) |
C16—C9—C10—O1 | 174.51 (16) | C20—C21—C22—C23 | 1.0 (3) |
C17—C9—C10—O1 | −60.1 (2) | C21—C22—C23—C24 | −1.0 (3) |
N1—C9—C10—N2 | −124.69 (15) | C22—C23—C24—C19 | −0.2 (3) |
C16—C9—C10—N2 | −5.07 (16) | C20—C19—C24—C23 | 1.3 (2) |
C17—C9—C10—N2 | 120.37 (14) | C18—C19—C24—C23 | 177.76 (16) |
C16—C11—C12—C13 | 1.3 (3) | C18—C17—C25—O2 | 146.81 (16) |
N2—C11—C12—C13 | −174.74 (19) | C7—C17—C25—O2 | 17.8 (2) |
C11—C12—C13—C14 | −0.2 (3) | C9—C17—C25—O2 | −92.85 (18) |
C12—C13—C14—C15 | −0.1 (3) | C18—C17—C25—O3 | −35.14 (17) |
C13—C14—C15—C16 | −0.7 (3) | C7—C17—C25—O3 | −164.13 (12) |
C14—C15—C16—C11 | 1.8 (2) | C9—C17—C25—O3 | 85.20 (14) |
C14—C15—C16—C9 | 176.90 (16) | C7—C8—N1—C27 | −169.79 (15) |
C12—C11—C16—C15 | −2.2 (3) | C7—C8—N1—C9 | −42.64 (17) |
N2—C11—C16—C15 | 174.60 (15) | C16—C9—N1—C8 | 167.99 (14) |
C12—C11—C16—C9 | −178.24 (16) | C10—C9—N1—C8 | −78.71 (17) |
N2—C11—C16—C9 | −1.49 (19) | C17—C9—N1—C8 | 40.32 (16) |
N1—C9—C16—C15 | −50.5 (2) | C16—C9—N1—C27 | −65.99 (18) |
C10—C9—C16—C15 | −171.62 (17) | C10—C9—N1—C27 | 47.31 (19) |
C17—C9—C16—C15 | 68.6 (2) | C17—C9—N1—C27 | 166.33 (14) |
N1—C9—C16—C11 | 125.01 (14) | O1—C10—N2—C11 | −174.94 (16) |
C10—C9—C16—C11 | 3.87 (16) | C9—C10—N2—C11 | 4.64 (19) |
C17—C9—C16—C11 | −115.93 (15) | C12—C11—N2—C10 | 174.33 (18) |
C6—C7—C17—C25 | 117.36 (15) | C16—C11—N2—C10 | −2.1 (2) |
C8—C7—C17—C25 | −115.37 (14) | O2—C25—O3—C26 | −1.2 (2) |
C6—C7—C17—C18 | −8.4 (2) | C17—C25—O3—C26 | −179.28 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O1 | 0.97 | 2.31 | 3.046 (2) | 132 |
C24—H24···O3 | 0.93 | 2.52 | 3.155 (2) | 126 |
N2—H2A···O2i | 0.86 | 2.07 | 2.924 (2) | 170 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18B···O1 | 0.97 | 2.31 | 3.046 (2) | 132 |
C24—H24···O3 | 0.93 | 2.52 | 3.155 (2) | 126 |
N2—H2A···O2i | 0.86 | 2.07 | 2.924 (2) | 170.02 |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.
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.
The derivatives of spiro-oxindole ring systems are used as antimicrobial, antitumor agents and as inhibitors of the human NKI receptor besides being found in a number of alkaloids like horsifiline, spirotryprostatin and (+)elacomine (Hilton et al., 2000).
The molecular structure of the title compound is illustrated in Fig 1. In the molecule, there are C—H···O hydrogen bonds forming S(6) and S(7) ring motifs (Bernstein et al., 1995), and a π···π interaction [Cg(1)···Cg(2) = 3.6291 (11) Å, where Cg1 and Cg2 are the centroids of rings C1—C6 and C19—C24, respectively]. The indole ring system is essentially planar with a maximum deviation of 0.082 (2) Å for atom C10. The mean plane of this indole ring system forms a dihedral angle of 88.53 (6)° with the 4-methylpyrrolidine ring mean plane. The latter forms a dihedral angle of 83.37 (9)° with the benzyl ring which shows that they are almost orthogonal. Atom O1 significantly deviates from the mean plane of the indole ring system by -0.2251 (15) Å. The molecular dimensions in the title compound are in excellent agreement with those reported for the 3-bromophenyl derivative (Karthikeyan et al., 2014).
The spiro-pyrrolidine ring (N1/C7-C9/C17) adopts an envelope conformation with atom N1 at the flap. The distance to the flap position from the mean plane of the four C atoms is 0.2476 (16) Å; the ring puckering parameters (Cremer & Pople, 1975) are Q2 = 0.3917 (18) Å and φ2 = 2.8 (3)°. The central spiro-pyrrolidine ring mean plane is perpendicular to the dichlorophenyl ring with a dihedral angle of 81.66 (9)°. The carbonyl group, C10═O2, and the benzyl ring (C18-C24) ring have an (+)anti-clinal conformation with torsion angle (C18—C17—C25—O2) of 146.81 (16)°.
In the benzene ring (C11—C16) of the indole ring system, the expansion of the ipso angles at C11, C13 and C14 [121.71 (19), 121.1 (2) and 120.8 (2)°, respectively] and contraction of the apical angles at C12, C15 and C16 [117.9 (2), 119.13 (18) and 119.43 (16)°, respectively] are caused by the fusion of the smaller pyrrole ring to the six-membered benzene ring and the strain is taken up by the angular distortion rather than by bond-length distortions (Allen, 1981). The carboxyl group and oxindole ring system are (-)anti-clinal to each other with torsion angle (C9—C17—C25—O2) of -92.85 (18)°.
In the crystal, molecules are linked via N-H···O hydrogen bonds forming C(7) chains running parallel to [1 0 -1]; see Fig. 2 and Table 1.