2-(1-Hexyl-2-oxo-2,3-di­hydro-1H-indol-3-yl­idene)propanedi­nitrile

Rayni, I.; El Bakri, Y.; Sebhaoui, J.; El Bourakadi, K.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314617007064

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170706

https://doi.org/10.1107/S2414314617007064

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2-(1-Hexyl-2-oxo-2,3-dihydro-1H-indol-3-ylidene)propanedinitrile

Ibtissam Rayni,^a ^* Youness El Bakri,^a Jihad Sebhaoui,^a Khadija El Bourakadi,^a El Mokhtar Essassi ^a and Joel T. Mague ^b

^aLaboratoire de Chimie Organique Hétérocyclique, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Mohammed V University, Rabat, Morocco, and ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: irayni@yahoo.fr

Edited by J. Simpson, University of Otago, New Zealand (Received 9 May 2017; accepted 11 May 2017; online 16 May 2017)

In the title compound, C₁₇H₁₇N₃O, the indolone ring system is almost planar, with an angle of 0.76 (14)° between the five- and six-membered rings. The dicyanomethylidene substituent lies close to the indolene plane. In the crystal, offset π-stacking interactions between five- and six-membered rings of indolene stack the molecules along the c-axis direction.

Keywords: crystal structure; indolone; π-stacking.

CCDC reference: 1549179

Structure description

Oxindole derivatives are used in a wide range of biological applications, including as NMDA antagonists (Kang et al., 2002 ) and calcium channel blockers (Swensen et al., 2012 ), as well as having antiangiogenic (Whatmore et al., 2002 ) and anticancer properties (Peddibhotla, 2009 ). In a continuaton of our previous research on the synthesis of new heterocyclic systems containing the oxindole unit (Alsubari et al., 2009 ; Al Mamari et al., 2012 ), we report here the synthesis and the crystal structure of the title compound (Fig. 1).

Figure 1
The title molecule, showing the atom-labelling scheme and 50% probability displacement ellipsoids.

The bicyclic portion of the molecule is almost planar with the five- and six-membered rings inclined to one another by 0.76 (14)°. The dicyanomethylidene substituent is with this ring system, as indicated by the C6—C7—C9—C10 torsion angle of −1.5 (5)°.

In the crystal, the indolone units stack along the c-axis direction as a result of π–π stacking interactions between the five- and six-membered rings (Fig. 2), with Cg1⋯Cg2ⁱ = Cg1ⁱⁱ⋯Cg2 = 3.6985 (18) Å. The stacking is such that the n-hexyl chains all point in the same direction and are arranged one on top of the other (Fig. 3).

Figure 2
Detail of the π-stacking interactions. Cg1 and Cg2 are, respectively, the centroids of the five- and six-membered rings. [Symmetry codes: (i) x, y, z + 1; (ii) x, y, z − 1.]

Figure 3
The packing viewed along the c-axis direction.

Synthesis and crystallization

A mixture of 1-hexyl-1H-indol-2,3-dione (0.5 g, 2.1 mmol), malononitrile (0.14 g, 2.1 mmol) and iodine (0.05 g, 0.21 mmol) in ethanol (10 ml), was heated at 333 K for appropriately 1 h. The reaction was monitored by thin-layer chromatography. After completion, the mixture was treated with aqueous Na₂S₂O₃ solution, extracted with ethyl acetate (2 × 10 ml). The extract was dried over sodium sulfate, filtered and the solvent was evaporated under reduced pressure. The product obtained was recrystallized from an ethanol solution to afford the title compound as orange plate-like crystals.

Refinement

Crystal and refinement details appear in Table 1. Independent refinement of the H atoms attached to C17 did not result in a satisfactory geometry for the methyl group so these H atoms were included as riding contributions in idealized positions. The absolute structure could not be determined with certainty.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₇H₁₇N₃O
M_r	279.33
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	12.0350 (5), 24.5052 (9), 4.9909 (2)
V (Å³)	1471.92 (10)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.64
Crystal size (mm)	0.31 × 0.12 × 0.03

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.86, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	10951, 2456, 2293
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.114, 1.08
No. of reflections	2456
No. of parameters	247
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.19
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1549179

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617007064/sj4112sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617007064/sj4112Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617007064/sj4112Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617007064/sj4112Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-(1-Hexyl-2-oxo-2,3-dihydro-1H-indol-3-ylidene)propanedinitrile top

Crystal data top

C₁₇H₁₇N₃O	D_x = 1.261 Mg m⁻³
M_r = 279.33	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pna2₁	Cell parameters from 9234 reflections
a = 12.0350 (5) Å	θ = 3.6–72.6°
b = 24.5052 (9) Å	µ = 0.64 mm⁻¹
c = 4.9909 (2) Å	T = 150 K
V = 1471.92 (10) Å³	Plate, orange
Z = 4	0.31 × 0.12 × 0.03 mm
F(000) = 592

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2456 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2293 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.050
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.7°, θ_min = 3.6°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −30→26
T_min = 0.86, T_max = 0.98	l = −6→5
10951 measured reflections

Refinement top

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)] = 0.045	Hydrogen site location: mixed
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0724P)² + 0.2296P] where P = (F_o² + 2F_c²)/3
2456 reflections	(Δ/σ)_max < 0.001
247 parameters	Δρ_max = 0.38 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. Independent refinement of the hydrogen atoms attached to C17 did not result in a satisfactory geometry for the methyl group so these hydroges were inclused as riding contributions in idealized positions. The absolute structure could not be determined with certainty.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.43707 (17)	0.23427 (8)	0.8224 (5)	0.0360 (5)
N1	0.57751 (17)	0.23919 (8)	0.5072 (5)	0.0253 (5)
N2	0.4030 (2)	0.02200 (11)	0.4344 (7)	0.0404 (7)
N3	0.2816 (2)	0.13700 (11)	1.0310 (6)	0.0380 (6)
C1	0.6233 (2)	0.20390 (10)	0.3149 (6)	0.0226 (6)
C2	0.7104 (2)	0.21380 (11)	0.1406 (6)	0.0273 (6)
H2	0.754 (3)	0.2494 (13)	0.128 (8)	0.034 (9)*
C3	0.7402 (2)	0.17153 (12)	−0.0332 (6)	0.0296 (6)
H3	0.800 (3)	0.1766 (14)	−0.155 (9)	0.036 (9)*
C4	0.6858 (2)	0.12108 (12)	−0.0306 (7)	0.0297 (6)
H4	0.707 (3)	0.0939 (15)	−0.151 (9)	0.037 (9)*
C5	0.5998 (2)	0.11140 (11)	0.1507 (6)	0.0253 (6)
H5	0.562 (3)	0.0746 (13)	0.145 (8)	0.027 (8)*
C6	0.56841 (19)	0.15300 (10)	0.3244 (6)	0.0217 (5)
C7	0.48545 (19)	0.15684 (10)	0.5328 (6)	0.0230 (5)
C8	0.4937 (2)	0.21416 (11)	0.6448 (6)	0.0263 (6)
C9	0.41289 (19)	0.11947 (11)	0.6307 (6)	0.0247 (6)
C10	0.4070 (2)	0.06503 (12)	0.5225 (7)	0.0308 (6)
C11	0.3402 (2)	0.13069 (11)	0.8536 (6)	0.0286 (6)
C12	0.6099 (2)	0.29548 (11)	0.5559 (7)	0.0283 (6)
H12A	0.611 (3)	0.3029 (16)	0.756 (9)	0.045 (11)*
H12B	0.690 (3)	0.3001 (15)	0.493 (9)	0.047 (10)*
C13	0.5359 (2)	0.33637 (11)	0.4133 (6)	0.0262 (6)
H13A	0.455 (3)	0.3282 (13)	0.473 (8)	0.032 (8)*
H13B	0.543 (3)	0.3296 (15)	0.234 (9)	0.038 (10)*
C14	0.5682 (2)	0.39492 (11)	0.4838 (7)	0.0281 (6)
H14A	0.564 (3)	0.3969 (14)	0.707 (8)	0.034 (9)*
H14B	0.644 (3)	0.4013 (17)	0.415 (9)	0.054 (12)*
C15	0.4910 (2)	0.43796 (10)	0.3688 (6)	0.0276 (6)
H15A	0.480 (3)	0.4318 (16)	0.158 (10)	0.054 (12)*
H15B	0.529 (3)	0.4761 (15)	0.403 (9)	0.042 (10)*
C16	0.3748 (2)	0.43823 (11)	0.4915 (7)	0.0292 (6)
H16A	0.386 (4)	0.4422 (16)	0.692 (10)	0.050 (11)*
H16B	0.338 (3)	0.4034 (14)	0.448 (7)	0.033 (9)*
C17	0.3042 (2)	0.48580 (12)	0.3981 (8)	0.0369 (7)
H17A	0.2310	0.4839	0.4838	0.055*
H17B	0.2953	0.4841	0.2031	0.055*
H17C	0.3406	0.5202	0.4469	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0386 (11)	0.0338 (11)	0.0357 (13)	0.0015 (9)	0.0127 (10)	−0.0065 (9)
N1	0.0279 (10)	0.0208 (11)	0.0272 (13)	−0.0012 (8)	0.0058 (10)	−0.0009 (9)
N2	0.0466 (14)	0.0266 (12)	0.0480 (18)	−0.0084 (11)	0.0080 (13)	0.0004 (12)
N3	0.0358 (12)	0.0448 (15)	0.0335 (15)	−0.0027 (11)	0.0075 (13)	0.0050 (12)
C1	0.0231 (11)	0.0216 (12)	0.0231 (14)	0.0015 (10)	0.0004 (10)	0.0002 (10)
C2	0.0264 (12)	0.0294 (13)	0.0262 (15)	−0.0021 (10)	0.0041 (12)	0.0047 (12)
C3	0.0245 (11)	0.0352 (14)	0.0291 (16)	0.0025 (11)	0.0061 (12)	0.0033 (13)
C4	0.0302 (13)	0.0298 (13)	0.0290 (16)	0.0055 (11)	0.0050 (12)	−0.0030 (12)
C5	0.0245 (11)	0.0248 (13)	0.0265 (15)	0.0020 (10)	0.0005 (11)	−0.0001 (12)
C6	0.0193 (11)	0.0214 (12)	0.0245 (14)	0.0013 (9)	0.0002 (10)	0.0027 (10)
C7	0.0238 (11)	0.0232 (12)	0.0221 (13)	0.0020 (9)	0.0006 (10)	0.0008 (11)
C8	0.0270 (11)	0.0260 (12)	0.0258 (14)	0.0015 (10)	0.0016 (12)	−0.0005 (12)
C9	0.0221 (11)	0.0282 (13)	0.0238 (14)	−0.0009 (9)	0.0020 (11)	0.0041 (11)
C10	0.0292 (12)	0.0307 (14)	0.0324 (16)	−0.0047 (10)	0.0047 (12)	0.0063 (13)
C11	0.0246 (12)	0.0320 (14)	0.0292 (16)	−0.0008 (10)	0.0006 (12)	0.0059 (12)
C12	0.0305 (12)	0.0224 (13)	0.0320 (17)	−0.0010 (10)	−0.0017 (12)	−0.0044 (11)
C13	0.0312 (13)	0.0224 (12)	0.0249 (15)	−0.0002 (10)	−0.0010 (11)	−0.0016 (11)
C14	0.0269 (12)	0.0226 (12)	0.0347 (17)	−0.0007 (10)	0.0053 (12)	−0.0032 (12)
C15	0.0331 (14)	0.0205 (12)	0.0291 (16)	−0.0015 (10)	0.0049 (12)	0.0050 (12)
C16	0.0288 (12)	0.0255 (13)	0.0333 (17)	−0.0007 (11)	0.0017 (12)	0.0006 (12)
C17	0.0323 (14)	0.0287 (14)	0.050 (2)	0.0023 (12)	−0.0044 (14)	0.0024 (14)

Geometric parameters (Å, º) top

O1—C8	1.222 (4)	C9—C11	1.442 (4)
N1—C8	1.365 (4)	C12—C13	1.518 (4)
N1—C1	1.405 (4)	C12—H12A	1.01 (4)
N1—C12	1.454 (3)	C12—H12B	1.02 (4)
N2—C10	1.144 (4)	C13—C14	1.527 (4)
N3—C11	1.142 (4)	C13—H13A	1.03 (3)
C1—C2	1.383 (4)	C13—H13B	0.91 (4)
C1—C6	1.412 (4)	C14—C15	1.518 (4)
C2—C3	1.398 (4)	C14—H14A	1.12 (4)
C2—H2	1.02 (3)	C14—H14B	0.99 (4)
C3—C4	1.399 (4)	C15—C16	1.526 (4)
C3—H3	0.95 (4)	C15—H15A	1.07 (5)
C4—C5	1.395 (4)	C15—H15B	1.06 (4)
C4—H4	0.93 (4)	C16—C17	1.516 (4)
C5—C6	1.390 (4)	C16—H16A	1.02 (5)
C5—H5	1.01 (3)	C16—H16B	0.99 (3)
C6—C7	1.445 (4)	C17—H17A	0.9800
C7—C9	1.357 (4)	C17—H17B	0.9800
C7—C8	1.515 (4)	C17—H17C	0.9800
C9—C10	1.441 (4)

C8—N1—C1	110.9 (2)	C13—C12—H12A	111 (2)
C8—N1—C12	122.7 (2)	N1—C12—H12B	108 (2)
C1—N1—C12	126.4 (2)	C13—C12—H12B	110 (2)
C2—C1—N1	128.2 (2)	H12A—C12—H12B	106 (3)
C2—C1—C6	122.0 (3)	C12—C13—C14	111.3 (2)
N1—C1—C6	109.7 (2)	C12—C13—H13A	107 (2)
C1—C2—C3	117.0 (2)	C14—C13—H13A	110.7 (19)
C1—C2—H2	125 (2)	C12—C13—H13B	107 (2)
C3—C2—H2	118 (2)	C14—C13—H13B	112 (2)
C2—C3—C4	121.9 (3)	H13A—C13—H13B	110 (3)
C2—C3—H3	120 (2)	C15—C14—C13	114.2 (2)
C4—C3—H3	118 (2)	C15—C14—H14A	108.5 (19)
C5—C4—C3	120.2 (3)	C13—C14—H14A	105.0 (18)
C5—C4—H4	120 (2)	C15—C14—H14B	109 (2)
C3—C4—H4	120 (2)	C13—C14—H14B	108 (2)
C6—C5—C4	118.8 (2)	H14A—C14—H14B	113 (3)
C6—C5—H5	124 (2)	C14—C15—C16	114.3 (2)
C4—C5—H5	118 (2)	C14—C15—H15A	110 (2)
C5—C6—C1	120.0 (2)	C16—C15—H15A	107 (2)
C5—C6—C7	133.2 (2)	C14—C15—H15B	107 (2)
C1—C6—C7	106.9 (2)	C16—C15—H15B	109 (2)
C9—C7—C6	131.3 (3)	H15A—C15—H15B	110 (3)
C9—C7—C8	122.4 (2)	C17—C16—C15	113.2 (2)
C6—C7—C8	106.3 (2)	C17—C16—H16A	107 (2)
O1—C8—N1	126.6 (3)	C15—C16—H16A	106 (3)
O1—C8—C7	127.2 (3)	C17—C16—H16B	110.2 (19)
N1—C8—C7	106.2 (2)	C15—C16—H16B	108.7 (19)
C7—C9—C10	121.4 (3)	H16A—C16—H16B	111 (3)
C7—C9—C11	122.7 (3)	C16—C17—H17A	109.5
C10—C9—C11	115.8 (2)	C16—C17—H17B	109.5
N2—C10—C9	179.3 (3)	H17A—C17—H17B	109.5
N3—C11—C9	176.8 (3)	C16—C17—H17C	109.5
N1—C12—C13	113.0 (2)	H17A—C17—H17C	109.5
N1—C12—H12A	110 (2)	H17B—C17—H17C	109.5

C8—N1—C1—C2	−178.7 (3)	C1—N1—C8—O1	−179.2 (3)
C12—N1—C1—C2	2.8 (5)	C12—N1—C8—O1	−0.7 (5)
C8—N1—C1—C6	−0.3 (3)	C1—N1—C8—C7	0.7 (3)
C12—N1—C1—C6	−178.7 (3)	C12—N1—C8—C7	179.2 (2)
N1—C1—C2—C3	−179.9 (3)	C9—C7—C8—O1	−2.6 (5)
C6—C1—C2—C3	1.8 (4)	C6—C7—C8—O1	179.0 (3)
C1—C2—C3—C4	−0.7 (4)	C9—C7—C8—N1	177.5 (3)
C2—C3—C4—C5	−0.7 (4)	C6—C7—C8—N1	−0.9 (3)
C3—C4—C5—C6	1.0 (4)	C6—C7—C9—C10	−1.5 (5)
C4—C5—C6—C1	0.0 (4)	C8—C7—C9—C10	−179.5 (3)
C4—C5—C6—C7	−179.6 (3)	C6—C7—C9—C11	176.2 (3)
C2—C1—C6—C5	−1.5 (4)	C8—C7—C9—C11	−1.8 (4)
N1—C1—C6—C5	179.9 (2)	C8—N1—C12—C13	−81.7 (3)
C2—C1—C6—C7	178.2 (3)	C1—N1—C12—C13	96.6 (3)
N1—C1—C6—C7	−0.4 (3)	N1—C12—C13—C14	176.4 (2)
C5—C6—C7—C9	2.2 (5)	C12—C13—C14—C15	−174.6 (3)
C1—C6—C7—C9	−177.5 (3)	C13—C14—C15—C16	68.5 (3)
C5—C6—C7—C8	−179.5 (3)	C14—C15—C16—C17	173.0 (3)
C1—C6—C7—C8	0.8 (3)

Acknowledgements

The support of NSF-MRI Grant #1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

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