5-Chloro-1-methyl­indoline-2,3-dione

Tribak, Z.; Kandri Rodi, Y.; Haoudi, A.; Essassi, E.M.; Capet, F.; Zouihri, H.

doi:10.1107/S2414314616009135

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160913

doi:10.1107/S2414314616009135

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5-Chloro-1-methylindoline-2,3-dione

Zineb Tribak,^a Youssef Kandri Rodi,^a Amal Haoudi,^a ^* El Mokhtar Essassi,^b Frédéric Capet ^c and Hafid Zouihri ^d

^aLaboratoire de Chimie Organique Appliquée-Chimie Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fès, Morocco, ^bLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014, Avenue Ibn Batouta, Rabat, Morocco, ^cUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181., Ecole Nationale Supérieure de Chimie de Lille, France, and ^dDépartement de Chimie, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, 80000 Agadir, Morocco
^*Correspondence e-mail: haoudi_amal@yahoo.fr

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 25 May 2016; accepted 6 June 2016; online 10 June 2016)

The title molecule, C₉H₆ClNO₂, is almost planar, with an r.m.s. deviation of the fitted non-hydrogen atoms of 0.0922 (19) Å. In the crystal, molecules are connected through methyl-C—H⋯O(carbonyl) interactions into supramolecular helical chains along the b axis. Inter-chain π–π interactions lead to layers parallel to the ab plane [centroid–centroid distances = 3.4861 (13) to 3.9767 (12) Å]. The crystal studied was a non-merohedral twin with a ratio of the twin components of 0.8612 (12): 0.1388 (12).

Keywords: crystal structure; indoline; C—H⋯O interactions.

CCDC reference: 1483751

Structure description

5-Chloro-1H-indole-2,3-dione is a derivative of isatin (1H-Indole-2,3-dione) which has several interesting activities such as anti-tubercular (Aboul-Fadl et al., 2010 ), cytotoxicity (Subba Reddy et al., 2012 ) anti-inflammatory, (Anisetti et al.; 2012 ) anti-convulsant (Eggadi et al., 2013 ) anxiolytic (Silva et al., 2013 ) and anti-depressant (Radhika et al., 2012 ).

The title compound (Fig. 1) was synthesized by the alkylation method (Kharbach et al., 2015 ) under phase-transfer catalysis conditions (Bouhfid et al., 2005 ). The crystal studied was a non-merohedral twin with a ratio of the twin components of 0.8612 (12): 0.1388 (12).

Figure 1
The molecular structure of the title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

The title molecule, C₉H₆ClNO₂, is almost planar, with an r.m.s. deviation of 0.0922 (19) Å. In the crystal, molecules are connected through methyl--carbonyl C—H⋯O interactions (Table 1) into infinite chains along the b axis. The packing (Fig. 2) is also influenced by inter-chain π–π interactions, which form layers parallel to the ab plane [centroid–centroid distances = 3.4861 (13) to 3.9767 (12) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9C⋯O2ⁱ	0.96	2.52	3.435 (3)	159
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
The crystal structure of the title compound, viewed along the a axis, showing chains parallel to the b axis linked by C—H⋯O hydrogen bonds (dashed lines). For the sake of clarity, H atoms not involved in the hydrogen bonds have been omitted.

Synthesis and crystallization

To a solution of 5-chloro-1H-indole-2,3-dione (0.4 g, 2.20 mmol) in DMF (25 ml), were added potassium carbonate (0.5 g, 3.3 mmol), tetra-n-butylammonium fluoride (0.1 g, 0,3 mmol) and methyl iodide (0.13 ml, 2.42 mmol). The reaction mixture was stirred at ambient temperature for 48 h. The precipitate was filtered and processed yielding the title compound in a good yield of 89% in the form of red crystals (m.p. 361 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. At the final stage of refinement, an analysis of the data using the TwinRotMat routine in PLATON (Spek, 2009 ) revealed a minor twin (twofold axis around c*). The twin matrix is (−0.999 0 0.002, 0 − 1 0, 1 0 0.999).

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₆ClNO₂
M_r	195.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	300
a, b, c (Å)	3.9766 (4), 11.9503 (13), 17.947 (2)
β (°)	96.163 (3)
V (Å³)	847.94 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.41
Crystal size (mm)	0.29 × 0.11 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.697, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12975, 2080, 1705
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.103, 1.05
No. of reflections	2080
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2009), XT (Sheldrick, 2015a ), SHELXL2015 (Sheldrick, 2015b ), PLATON (Spek, 2009) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1483751

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616009135/tk4016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616009135/tk4016Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616009135/tk4016Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: XT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

5-Chloro-1-methylindoline-2,3-dione top

Crystal data top

C₉H₆ClNO₂	F(000) = 400
M_r = 195.60	D_x = 1.532 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 3.9766 (4) Å	Cell parameters from 4975 reflections
b = 11.9503 (13) Å	θ = 2.9–25.6°
c = 17.947 (2) Å	µ = 0.41 mm⁻¹
β = 96.163 (3)°	T = 300 K
V = 847.94 (16) Å³	Prism, red
Z = 4	0.29 × 0.11 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	1705 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.027
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 28.3°, θ_min = 1.7°
T_min = 0.697, T_max = 0.746	h = −5→5
12975 measured reflections	k = −15→15
2080 independent reflections	l = −22→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0449P)² + 0.264P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2080 reflections	Δρ_max = 0.25 e Å⁻³
120 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.19046 (16)	0.83313 (5)	0.57429 (3)	0.06020 (19)
N1	0.7031 (5)	0.74151 (13)	0.28515 (9)	0.0445 (4)
O2	0.9524 (5)	0.58155 (13)	0.24499 (10)	0.0701 (5)
C1	0.5640 (5)	0.77475 (14)	0.35050 (10)	0.0384 (4)
O1	0.7708 (6)	0.49696 (13)	0.38997 (10)	0.0740 (5)
C2	0.4421 (5)	0.87931 (15)	0.36668 (11)	0.0436 (4)
H2	0.4393	0.9377	0.3324	0.052*
C6	0.5649 (5)	0.68680 (14)	0.40190 (11)	0.0417 (4)
C3	0.3238 (5)	0.89379 (16)	0.43616 (11)	0.0449 (5)
H3	0.2388	0.9631	0.4485	0.054*
C4	0.3301 (5)	0.80689 (16)	0.48740 (11)	0.0439 (4)
C8	0.8099 (6)	0.63366 (16)	0.29043 (12)	0.0509 (5)
C5	0.4483 (5)	0.70138 (16)	0.47102 (12)	0.0459 (5)
H5	0.4490	0.6429	0.5052	0.055*
C9	0.7425 (7)	0.81520 (18)	0.22215 (12)	0.0552 (5)
H9A	0.5238	0.8390	0.2000	0.083*
H9B	0.8562	0.7758	0.1855	0.083*
H9C	0.8736	0.8794	0.2394	0.083*
C7	0.7167 (6)	0.59026 (15)	0.36734 (13)	0.0507 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0628 (4)	0.0650 (4)	0.0544 (3)	0.0064 (3)	0.0138 (3)	−0.0002 (2)
N1	0.0503 (10)	0.0335 (7)	0.0492 (9)	−0.0035 (7)	0.0036 (8)	−0.0052 (7)
O2	0.0883 (13)	0.0505 (9)	0.0740 (10)	0.0077 (9)	0.0199 (11)	−0.0168 (8)
C1	0.0363 (9)	0.0325 (8)	0.0448 (9)	−0.0052 (7)	−0.0027 (8)	−0.0043 (7)
O1	0.1058 (15)	0.0303 (7)	0.0867 (12)	0.0099 (8)	0.0146 (12)	0.0037 (7)
C2	0.0494 (11)	0.0317 (8)	0.0475 (10)	0.0028 (8)	−0.0041 (9)	0.0022 (8)
C6	0.0418 (10)	0.0287 (8)	0.0532 (11)	−0.0032 (7)	−0.0013 (9)	−0.0009 (7)
C3	0.0441 (10)	0.0355 (9)	0.0538 (11)	0.0067 (8)	−0.0014 (10)	−0.0053 (8)
C4	0.0389 (10)	0.0451 (10)	0.0471 (10)	−0.0009 (8)	0.0021 (9)	−0.0017 (8)
C8	0.0550 (12)	0.0362 (9)	0.0605 (12)	−0.0035 (9)	0.0019 (11)	−0.0122 (9)
C5	0.0476 (11)	0.0358 (9)	0.0532 (12)	−0.0024 (8)	0.0005 (10)	0.0064 (8)
C9	0.0688 (15)	0.0495 (11)	0.0478 (11)	−0.0051 (11)	0.0090 (11)	0.0000 (9)
C7	0.0577 (13)	0.0313 (9)	0.0619 (12)	−0.0023 (9)	0.0004 (11)	−0.0037 (9)

Geometric parameters (Å, º) top

Cl1—C4	1.739 (2)	C6—C5	1.381 (3)
N1—C1	1.407 (3)	C6—C7	1.470 (3)
N1—C8	1.357 (3)	C3—H3	0.9300
N1—C9	1.455 (3)	C3—C4	1.386 (3)
O2—C8	1.214 (3)	C4—C5	1.388 (3)
C1—C2	1.382 (3)	C8—C7	1.556 (3)
C1—C6	1.398 (3)	C5—H5	0.9300
O1—C7	1.198 (2)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C2—C3	1.390 (3)	C9—H9C	0.9600

C1—N1—C9	124.18 (16)	C5—C4—Cl1	120.11 (16)
C8—N1—C1	110.98 (17)	N1—C8—C7	106.02 (17)
C8—N1—C9	124.77 (18)	O2—C8—N1	127.3 (2)
C2—C1—N1	127.50 (17)	O2—C8—C7	126.71 (19)
C2—C1—C6	121.13 (18)	C6—C5—C4	117.31 (18)
C6—C1—N1	111.37 (16)	C6—C5—H5	121.3
C1—C2—H2	121.3	C4—C5—H5	121.3
C1—C2—C3	117.46 (17)	N1—C9—H9A	109.5
C3—C2—H2	121.3	N1—C9—H9B	109.5
C1—C6—C7	106.48 (17)	N1—C9—H9C	109.5
C5—C6—C1	121.36 (17)	H9A—C9—H9B	109.5
C5—C6—C7	132.12 (18)	H9A—C9—H9C	109.5
C2—C3—H3	119.4	H9B—C9—H9C	109.5
C4—C3—C2	121.22 (17)	O1—C7—C6	130.9 (2)
C4—C3—H3	119.4	O1—C7—C8	124.0 (2)
C3—C4—Cl1	118.38 (15)	C6—C7—C8	105.09 (15)
C3—C4—C5	121.51 (19)

Cl1—C4—C5—C6	−178.13 (16)	C2—C1—C6—C7	−178.79 (18)
N1—C1—C2—C3	−178.3 (2)	C2—C3—C4—Cl1	177.88 (16)
N1—C1—C6—C5	178.22 (19)	C2—C3—C4—C5	−1.3 (3)
N1—C1—C6—C7	0.3 (2)	C6—C1—C2—C3	0.6 (3)
N1—C8—C7—O1	179.0 (2)	C3—C4—C5—C6	1.0 (3)
N1—C8—C7—C6	−2.1 (2)	C8—N1—C1—C2	177.2 (2)
O2—C8—C7—O1	−1.8 (4)	C8—N1—C1—C6	−1.7 (2)
O2—C8—C7—C6	177.2 (2)	C5—C6—C7—O1	2.3 (4)
C1—N1—C8—O2	−177.0 (2)	C5—C6—C7—C8	−176.6 (2)
C1—N1—C8—C7	2.3 (2)	C9—N1—C1—C2	0.2 (3)
C1—C2—C3—C4	0.4 (3)	C9—N1—C1—C6	−178.75 (19)
C1—C6—C5—C4	0.0 (3)	C9—N1—C8—O2	0.0 (4)
C1—C6—C7—O1	179.9 (3)	C9—N1—C8—C7	179.3 (2)
C1—C6—C7—C8	1.1 (2)	C7—C6—C5—C4	177.4 (2)
C2—C1—C6—C5	−0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9C···O2ⁱ	0.96	2.52	3.435 (3)	159

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

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