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Acta Cryst. (2008). E64, o834    [ doi:10.1107/S1600536808009446 ]

1-Allyl-3,3-diphenylindolin-2-one

S. Nirmala, E. T. S. Kamala, L. Sudha, A. R. N. Raj and C. A. M. A. Huq

Abstract top

In the title compound, C23H19NO, the oxindole residue is essentially planar and is almost perpendicular to the phenyl rings [dihedral angles = 72.1 (6) and 77.6 (6)°]. The molecular packing is stabilized by C-H...O hydrogen bonds and C-H...N interactions.

Comment top

Indole and its derivatives form a class of toxic recalcitrant N – heterocyclic compounds that are considered as pollutants (Florin et al., 1980). Derivatives of indole have received much attention because of their widespread applications in materials science, agrichemicals, and pharmaceuticals (Ramirez & Garcia-Rubio, 2003).Their preparation and functionalization continues to be a fascinating subject in organic synthesis due to the frequent appearance of indoles in biologically interesting compounds (Bandini et al., 2005). Compounds containing the indole moiety have been proven to display high activity of aldose reductase inhibition (Rajeswaran et al., 1999). In view of this importance, an X-ray study of the title compound, (I), was carried out.

An ORTEP (Farrugia,1997) plot of the molecule is shown in Fig.1. The indole moiety (N1/C2 – C9) is planar with the maximum deviation of 0.040 (8) for C2 atom. The oxindole ring is nearly orthogonal to phenyl rings A (C13 – C18) and B (C19 – C24), and makes a dihedral angle of 72.1 (6)° with the ring A, 77.6 (6)° with the ring B. Both the phenyl rings A and B are oriented at an angle of 70.4 (7)° with respect to each other. The sum of angles at N1 [360.0]° indicate sp2 hybridization. In the oxindole ring systems, the variation in endocyclic angles are due to fusion of five and six membered rings (Govind et al., 2003). The N1— C2 and C2— O1 bond lengths indicate electron delocalization over atoms N1, C2 and O1. The torsion angle C12—C11—C10—N1 = – 0.3 (4)° indicate that the allyl group deviates significantly from the plane of the attached indole moiety.

Weak intramolecular C—H···N and C—H··· π interactions stabilize the molecule. The crystal packing also involves inter molecular C—H···O interactions and van der Waals forces.

Related literature top

For related literature, see: Bandini et al. (2005); Florin et al. (1980); Govind et al. (2003); Rajeswaran et al. (1999); Ramirez & Garcia-Rubio (2003).

Experimental top

To a solution of phenyl magnesium bromide in dry THF, at 0°C under N2 atm.,1-N-allyl isatin (0.005 mol, 0.935 g), in dry THF, was added dropwise. After the complete addition, the mixture was stirred at 0°C for 1 hr and then it was stirred at room temperature for 5 hrs. The progress of the reaction was followed by TLC. On completion of the reaction, a saturated solution of NH4Cl was added slowly at 0°C. The aqueous layer was washed with brine (50 ml) and dried. On removal of the solvent under reduced pressure, a crude mass was obtained., which was purified over a column of silica gel (100–200 mesh) using hexane/ethyl acetate as eluent. Compound was recrystallized from methanol.

Refinement top

H atoms were placed in idealized positions and allowed to ride on their parent atoms with aromatic C—H distances of 0.93 Å, methylene C—H distances of 0.97 Å and with Uiso(H) = 1.2 Ueq(C).In the absence of significant anomalous scattering effects, Friedel pairs have been merged. The absolute structure parameter is removed from the CIF since the Flack [10.0 (10)] is meaningless.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids
[Figure 2] Fig. 2. The packing of the molecules viewed down a axis.
1-Allyl-3,3-diphenylindolin-2-one top
Crystal data top
C23H19NOF000 = 688
Mr = 325.39Dx = 1.230 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: p 2ac 2abCell parameters from 4984 reflections
a = 8.8449 (3) Åθ = 2.5–30.3º
b = 12.3879 (4) ŵ = 0.08 mm−1
c = 16.0377 (4) ÅT = 293 (2) K
V = 1757.25 (9) Å3Prism, yellow
Z = 40.30 × 0.24 × 0.20 mm
Data collection top
Bruker Kappa APEX2
diffractometer		3559 independent reflections
Radiation source: fine-focus sealed tube2611 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 293(2) Kθmax = 32.6º
ω and φ scansθmin = 2.5º
Absorption correction: multi-scan
(Blessing, 1995)		h = −13→11
Tmin = 0.978, Tmax = 0.985k = −18→14
14793 measured reflectionsl = −20→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.142  w = 1/[σ2(Fo2) + (0.0653P)2 + 0.2107P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
3559 reflectionsΔρmax = 0.31 e Å−3
226 parametersΔρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C23H19NOV = 1757.25 (9) Å3
Mr = 325.39Z = 4
Orthorhombic, P212121Mo Kα
a = 8.8449 (3) ŵ = 0.08 mm−1
b = 12.3879 (4) ÅT = 293 (2) K
c = 16.0377 (4) Å0.30 × 0.24 × 0.20 mm
Data collection top
Bruker Kappa APEX2
diffractometer		3559 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		2611 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.985Rint = 0.026
14793 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050Δρmax = 0.31 e Å−3
wR(F2) = 0.142Δρmin = −0.21 e Å−3
S = 1.09Absolute structure: ?
3559 reflectionsFlack parameter: ?
226 parametersRogers parameter: ?
H-atom parameters constrained
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C20.7623 (2)0.14099 (15)0.09508 (12)0.0367 (4)
C30.7846 (2)0.02597 (14)0.13122 (10)0.0331 (3)
C40.8751 (2)−0.02725 (15)0.06249 (11)0.0349 (4)
C50.9240 (3)−0.13195 (17)0.05340 (13)0.0454 (5)
H50.9017−0.18360.09370.055*
C61.0075 (3)−0.1595 (2)−0.01711 (14)0.0523 (5)
H61.0420−0.2299−0.02390.063*
C71.0390 (3)−0.0829 (2)−0.07656 (14)0.0570 (6)
H71.0952−0.1025−0.12310.068*
C80.9897 (3)0.0220 (2)−0.06920 (13)0.0517 (5)
H81.01190.0733−0.10970.062*
C90.9059 (2)0.04807 (16)0.00085 (11)0.0387 (4)
C100.8516 (3)0.24727 (19)−0.02570 (15)0.0543 (6)
H10A0.95270.2513−0.04900.065*
H10B0.84040.30730.01260.065*
C110.7411 (3)0.2612 (2)−0.09456 (17)0.0675 (7)
H110.74860.3252−0.12460.081*
C120.6406 (4)0.1988 (3)−0.1170 (2)0.0792 (9)
H12A0.62720.1334−0.08940.095*
H12B0.57810.2170−0.16140.095*
C130.8731 (2)0.03991 (15)0.21273 (11)0.0363 (4)
C140.8029 (3)0.08647 (16)0.28170 (13)0.0439 (4)
H140.70180.10670.27840.053*
C150.8814 (3)0.10282 (19)0.35467 (14)0.0534 (6)
H150.83270.13330.40040.064*
C161.0312 (3)0.0745 (2)0.36051 (15)0.0643 (7)
H161.08450.08630.40970.077*
C171.1015 (3)0.0285 (3)0.29290 (17)0.0782 (9)
H171.20280.00900.29640.094*
C181.0225 (3)0.0110 (3)0.21964 (15)0.0597 (6)
H181.0713−0.02080.17450.072*
C190.6328 (2)−0.03049 (15)0.14321 (11)0.0347 (4)
C200.5121 (2)−0.00927 (18)0.09117 (14)0.0446 (5)
H200.52210.04260.04960.054*
C210.3761 (3)−0.0640 (2)0.09980 (17)0.0548 (6)
H210.2957−0.04840.06450.066*
C220.3604 (3)−0.1413 (2)0.16061 (17)0.0572 (6)
H220.2690−0.17750.16690.069*
C230.4792 (3)−0.1650 (2)0.21185 (15)0.0596 (6)
H230.4688−0.21780.25260.072*
C240.6155 (3)−0.11038 (18)0.20325 (13)0.0500 (5)
H240.6961−0.12750.23810.060*
N10.8393 (2)0.14731 (13)0.02162 (10)0.0414 (4)
O10.69142 (19)0.21379 (12)0.12636 (10)0.0505 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0361 (9)0.0371 (9)0.0367 (8)−0.0015 (7)0.0006 (7)0.0024 (7)
C30.0331 (8)0.0371 (8)0.0290 (7)0.0005 (7)0.0027 (6)0.0012 (7)
C40.0326 (8)0.0408 (9)0.0313 (8)−0.0012 (7)0.0004 (7)−0.0026 (7)
C50.0469 (11)0.0442 (10)0.0452 (10)0.0025 (9)0.0027 (9)−0.0034 (9)
C60.0480 (12)0.0570 (12)0.0518 (12)0.0076 (10)0.0008 (10)−0.0170 (10)
C70.0455 (12)0.0809 (17)0.0446 (11)−0.0002 (11)0.0090 (10)−0.0169 (11)
C80.0486 (12)0.0700 (14)0.0363 (10)−0.0056 (11)0.0102 (9)0.0001 (10)
C90.0349 (9)0.0463 (9)0.0351 (8)−0.0051 (8)0.0027 (7)0.0006 (8)
C100.0559 (13)0.0514 (11)0.0557 (13)−0.0076 (10)0.0055 (11)0.0204 (11)
C110.0746 (17)0.0706 (17)0.0574 (15)0.0029 (15)−0.0022 (14)0.0130 (13)
C120.088 (2)0.084 (2)0.0650 (17)0.0092 (19)0.0007 (16)−0.0026 (15)
C130.0369 (9)0.0391 (9)0.0329 (8)−0.0001 (7)0.0011 (7)0.0000 (7)
C140.0458 (11)0.0473 (10)0.0386 (10)0.0052 (9)0.0013 (8)−0.0040 (8)
C150.0651 (15)0.0582 (13)0.0369 (10)0.0023 (12)0.0004 (10)−0.0089 (9)
C160.0631 (16)0.0861 (18)0.0437 (12)−0.0075 (14)−0.0126 (11)−0.0102 (12)
C170.0463 (13)0.126 (3)0.0618 (15)0.0108 (17)−0.0163 (12)−0.0218 (18)
C180.0395 (11)0.0917 (18)0.0479 (11)0.0075 (12)−0.0028 (9)−0.0165 (12)
C190.0354 (9)0.0368 (8)0.0319 (8)−0.0017 (7)0.0050 (6)0.0008 (7)
C200.0394 (10)0.0457 (10)0.0489 (11)0.0001 (8)0.0001 (8)0.0063 (9)
C210.0343 (10)0.0569 (13)0.0730 (15)−0.0010 (9)−0.0001 (10)−0.0082 (12)
C220.0471 (12)0.0530 (12)0.0713 (15)−0.0151 (10)0.0185 (11)−0.0132 (12)
C230.0773 (17)0.0548 (13)0.0468 (11)−0.0253 (12)0.0135 (12)0.0028 (10)
C240.0602 (14)0.0513 (12)0.0387 (10)−0.0141 (11)−0.0024 (9)0.0105 (9)
N10.0439 (9)0.0401 (8)0.0401 (8)−0.0042 (7)0.0052 (7)0.0081 (7)
O10.0565 (9)0.0411 (7)0.0539 (9)0.0091 (7)0.0066 (7)0.0007 (6)
Geometric parameters (Å, °) top
C2—O11.207 (2)C12—H12B0.9300
C2—N11.363 (2)C13—C181.374 (3)
C2—C31.551 (3)C13—C141.393 (3)
C3—C41.513 (2)C14—C151.376 (3)
C3—C191.526 (3)C14—H140.9300
C3—C131.533 (2)C15—C161.374 (4)
C4—C51.375 (3)C15—H150.9300
C4—C91.387 (3)C16—C171.373 (4)
C5—C61.393 (3)C16—H160.9300
C5—H50.9300C17—C181.384 (3)
C6—C71.374 (3)C17—H170.9300
C6—H60.9300C18—H180.9300
C7—C81.375 (4)C19—C201.380 (3)
C7—H70.9300C19—C241.389 (3)
C8—C91.384 (3)C20—C211.388 (3)
C8—H80.9300C20—H200.9300
C9—N11.404 (3)C21—C221.374 (4)
C10—N11.456 (3)C21—H210.9300
C10—C111.485 (4)C22—C231.366 (4)
C10—H10A0.9700C22—H220.9300
C10—H10B0.9700C23—C241.390 (3)
C11—C121.232 (4)C23—H230.9300
C11—H110.9300C24—H240.9300
C12—H12A0.9300
O1—C2—N1125.14 (18)C18—C13—C14118.21 (19)
O1—C2—C3126.65 (17)C18—C13—C3122.03 (18)
N1—C2—C3108.20 (15)C14—C13—C3119.73 (17)
C4—C3—C19110.95 (15)C15—C14—C13120.7 (2)
C4—C3—C13113.58 (15)C15—C14—H14119.6
C19—C3—C13113.16 (14)C13—C14—H14119.6
C4—C3—C2101.25 (14)C16—C15—C14120.5 (2)
C19—C3—C2110.88 (15)C16—C15—H15119.8
C13—C3—C2106.26 (14)C14—C15—H15119.8
C5—C4—C9119.81 (17)C17—C16—C15119.2 (2)
C5—C4—C3130.89 (17)C17—C16—H16120.4
C9—C4—C3109.29 (16)C15—C16—H16120.4
C4—C5—C6118.9 (2)C16—C17—C18120.5 (2)
C4—C5—H5120.5C16—C17—H17119.8
C6—C5—H5120.5C18—C17—H17119.8
C7—C6—C5120.1 (2)C13—C18—C17120.8 (2)
C7—C6—H6119.9C13—C18—H18119.6
C5—C6—H6119.9C17—C18—H18119.6
C6—C7—C8121.9 (2)C20—C19—C24118.03 (18)
C6—C7—H7119.0C20—C19—C3121.12 (16)
C8—C7—H7119.0C24—C19—C3120.69 (18)
C7—C8—C9117.4 (2)C19—C20—C21121.1 (2)
C7—C8—H8121.3C19—C20—H20119.4
C9—C8—H8121.3C21—C20—H20119.4
C8—C9—C4121.79 (19)C22—C21—C20119.9 (2)
C8—C9—N1128.49 (18)C22—C21—H21120.0
C4—C9—N1109.72 (16)C20—C21—H21120.0
N1—C10—C11115.9 (2)C23—C22—C21119.9 (2)
N1—C10—H10A108.3C23—C22—H22120.0
C11—C10—H10A108.3C21—C22—H22120.0
N1—C10—H10B108.3C22—C23—C24120.2 (2)
C11—C10—H10B108.3C22—C23—H23119.9
H10A—C10—H10B107.4C24—C23—H23119.9
C12—C11—C10128.2 (3)C19—C24—C23120.7 (2)
C12—C11—H11115.9C19—C24—H24119.6
C10—C11—H11115.9C23—C24—H24119.6
C11—C12—H12A120.0C2—N1—C9111.39 (15)
C11—C12—H12B120.0C2—N1—C10122.46 (18)
H12A—C12—H12B120.0C9—N1—C10126.12 (17)
O1—C2—C3—C4177.4 (2)C3—C13—C14—C15−177.99 (18)
N1—C2—C3—C4−3.70 (18)C13—C14—C15—C160.7 (4)
O1—C2—C3—C1959.6 (2)C14—C15—C16—C17−0.7 (4)
N1—C2—C3—C19−121.48 (16)C15—C16—C17—C180.1 (5)
O1—C2—C3—C13−63.8 (2)C14—C13—C18—C17−0.6 (4)
N1—C2—C3—C13115.17 (16)C3—C13—C18—C17177.3 (3)
C19—C3—C4—C5−57.8 (3)C16—C17—C18—C130.6 (5)
C13—C3—C4—C571.0 (3)C4—C3—C19—C20−80.4 (2)
C2—C3—C4—C5−175.6 (2)C13—C3—C19—C20150.58 (17)
C19—C3—C4—C9120.96 (17)C2—C3—C19—C2031.3 (2)
C13—C3—C4—C9−110.24 (17)C4—C3—C19—C2495.0 (2)
C2—C3—C4—C93.23 (18)C13—C3—C19—C24−34.0 (2)
C9—C4—C5—C61.6 (3)C2—C3—C19—C24−153.30 (18)
C3—C4—C5—C6−179.68 (19)C24—C19—C20—C211.6 (3)
C4—C5—C6—C7−0.5 (3)C3—C19—C20—C21177.17 (19)
C5—C6—C7—C8−0.3 (4)C19—C20—C21—C22−0.5 (4)
C6—C7—C8—C9−0.2 (4)C20—C21—C22—C23−0.7 (4)
C7—C8—C9—C41.4 (3)C21—C22—C23—C240.6 (4)
C7—C8—C9—N1−177.8 (2)C20—C19—C24—C23−1.7 (3)
C5—C4—C9—C8−2.2 (3)C3—C19—C24—C23−177.3 (2)
C3—C4—C9—C8178.88 (19)C22—C23—C24—C190.6 (4)
C5—C4—C9—N1177.21 (18)O1—C2—N1—C9−178.1 (2)
C3—C4—C9—N1−1.7 (2)C3—C2—N1—C93.0 (2)
N1—C10—C11—C12−0.3 (4)O1—C2—N1—C103.8 (3)
C4—C3—C13—C183.0 (3)C3—C2—N1—C10−175.20 (18)
C19—C3—C13—C18130.7 (2)C8—C9—N1—C2178.5 (2)
C2—C3—C13—C18−107.4 (2)C4—C9—N1—C2−0.8 (2)
C4—C3—C13—C14−179.13 (17)C8—C9—N1—C10−3.4 (4)
C19—C3—C13—C14−51.5 (2)C4—C9—N1—C10177.25 (19)
C2—C3—C13—C1470.4 (2)C11—C10—N1—C2−96.5 (3)
C18—C13—C14—C15−0.1 (3)C11—C10—N1—C985.6 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···N10.932.592.905 (4)100
C10—H10A···O1i0.972.493.446 (3)170
C23—H23···O1ii0.932.553.356 (3)146
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
C2—O11.207 (2)C9—N11.404 (3)
C2—N11.363 (2)C10—N11.456 (3)
O1—C2—N1125.14 (18)C4—C9—N1109.72 (16)
O1—C2—C3126.65 (17)N1—C10—C11115.9 (2)
N1—C2—C3108.20 (15)C2—N1—C9111.39 (15)
C5—C4—C9119.81 (17)C2—N1—C10122.46 (18)
C8—C9—C4121.79 (19)C9—N1—C10126.12 (17)
C8—C9—N1128.49 (18)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···N10.932.592.905 (4)100
C10—H10A···O1i0.972.493.446 (3)170
C23—H23···O1ii0.932.553.356 (3)146
Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) −x+1, y−1/2, −z+1/2.
Acknowledgements top

SN thanks Professor M. N. Ponnuswamy, Department of Crystallography and Biophysics, University of Madras, India, for his guidance and valuable suggestions. SN thanks SRM management, India, for their support.

references
References top

Bandini, M., Melloni, A., Tommasi, S. & Umani-Ronchi, A. (2005). Synlett, 8, 1199–1222.

Blessing, R. H. (1995). Acta Cryst. A51, 33–38.

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Florin, I., Rutberg, L., Curvall, M. & Enzell, C. R. (1980). Toxicology, 15, 219–232.

Govind, M. M., Selvanayagam, S., Velmurugan, D., Ravikumar, K., Sridhar, G. & Raghunathan, R. (2003). Acta Cryst. E59, o1438–o1440.

Rajeswaran, W. G., Labroo, R. B., Cohen, L. A. & King, M. M. (1999). J. Org. Chem. 64, 1369–1371.

Ramirez, A. & Garcia-Rubio, S. (2003). Curr. Med. Chem. 10 (18), 1891–1915.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.