6-Chloro-1-methyl­indoline-2,3-dione

Abstract

The title mol­ecule, C₉H₆ClNO₂, is essentially planar: the maximum deviation from the mean plane of the indoline ring is 0.020 (2) Å and the substituents do not deviate by more than 0.053 (2) Å from this plane. C—H⋯O hydrogen bonds help to consolidate the crystal structure.

Related literature

The title compound is a halogenated derivative of isatin. For the cytotoxic and anti­neoplastic activity of halogenated isatin deriv­atives, see: Vine et al. (2007 ▶); Matesic et al. (2008 ▶). For the preparation of the title compound, see: Bouhfid et al. (2005 ▶). For a related structure, see: Wu et al. (2011 ▶).

Experimental

Crystal data

• C₉H₆ClNO₂

• M _r = 195.60

• Monoclinic,

• a = 13.077 (3) Å

• b = 7.9390 (16) Å

• c = 16.673 (3) Å

• β = 101.95 (3)°

• V = 1693.5 (6) ų

• Z = 8

• Mo Kα radiation

• μ = 0.41 mm⁻¹

• T = 293 K

• 0.30 × 0.20 × 0.10 mm

Data collection

• Enraf–Nonius CAD-4 diffractometer

• Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.887, T _max = 0.960

• 3124 measured reflections

• 1557 independent reflections

• 1250 reflections with I > 2σ(I)

• R _int = 0.031

• 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.118

• S = 1.00

• 1557 reflections

• 119 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811051294/pv2487Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1i	0.93	2.50	3.419 (2)	168

Symmetry code: (i) .

supplementary crystallographic information

Comment

Halogenated derivatives of isatin have been reported to exhibit cytotoxic and antineoplastic activities (Vine et al., 2007; Matesic et al., 2008). As a part of our studies on the synthesis of isatin derivatives, the title compound was synthesized (Bouhfid et al. (2005)). We report herein the crystal structure of the title compound.

The title molecule (Fig. 1) is essentially planar with the maximum deviation of C4 atom from the mean-plane of indoline ring (N,C1–C8) is 0.020 (2) Å and the substituents do not deviate more than 0.053 (2) Å from this plane. In the crystal structure, intermolecular and intramolecular C—H···O hydrogen bonds helps to consolidate the crystal packing (Fig. 2 & Tab. 1).

Experimental

6-Chloroisatin (1.81 g, 0.01 mol) was reacted with iodomethane (0.02 mol) in the presence of K₂CO₃ (2.76 g, 0.02 mol) and tetrabutylammonium bromide (0.32 g, 0.001 mol) in DMF (60 ml). After 12 h stirring at room temperature, the precipitate was removed by filtration and purified by recrystallization from ethanol (m.p. 450–451 K; yield 67%). Yellow crystals of the title compound were obtained by slow evaporation from ethanol at room temperature.

Refinement

All H atoms were placed geometrically at the distances C—H = 0.93 and 0.96 Å for aryl and methyl type H-atoms and included in the refinement in riding motion approximation with U_iso(H) = 1.2 or 1.5U_eq(C).

Figures

Fig. 1.

The molecular structure of the title molecule showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.

Fig. 2.

A packing diagram of the title compound. The intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C9H6ClNO2	F(000) = 800
Mr = 195.60	Dx = 1.534 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 13.077 (3) Å	θ = 9–13°
b = 7.9390 (16) Å	µ = 0.41 mm−1
c = 16.673 (3) Å	T = 293 K
β = 101.95 (3)°	Block, yellow
V = 1693.5 (6) Å3	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer	1250 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
graphite	θmax = 25.4°, θmin = 2.5°
ω/2θ scans	h = 0→15
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
Tmin = 0.887, Tmax = 0.960	l = −20→20
3124 measured reflections	3 standard reflections every 200 reflections
1557 independent reflections	intensity decay: 1%

Refinement

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.080P)2] where P = (Fo2 + 2Fc2)/3
1557 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.17 e Å−3
1 restraint	Δρmin = −0.27 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.44670 (4)	0.16058 (8)	0.34958 (3)	0.0700 (3)
N	0.64277 (11)	0.39456 (19)	0.62790 (9)	0.0490 (4)
C1	0.62506 (13)	0.3717 (2)	0.54308 (11)	0.0427 (4)
O1	0.84333 (11)	0.63253 (19)	0.57603 (13)	0.0790 (5)
C2	0.54622 (13)	0.2784 (2)	0.49497 (11)	0.0441 (4)
H2A	0.4961	0.2225	0.5172	0.053*
O2	0.76431 (12)	0.5344 (2)	0.72436 (10)	0.0801 (5)
C3	0.54593 (14)	0.2728 (2)	0.41247 (12)	0.0492 (5)
C4	0.62028 (16)	0.3525 (2)	0.37645 (13)	0.0552 (5)
H4A	0.6180	0.3424	0.3205	0.066*
C5	0.69747 (15)	0.4469 (2)	0.42582 (13)	0.0554 (5)
H5A	0.7472	0.5033	0.4033	0.067*
C6	0.69983 (13)	0.4564 (2)	0.50844 (12)	0.0484 (5)
C7	0.76899 (14)	0.5415 (2)	0.57711 (15)	0.0579 (5)
C8	0.72891 (14)	0.4939 (2)	0.65333 (14)	0.0579 (5)
C9	0.58013 (17)	0.3220 (3)	0.68150 (14)	0.0608 (5)
H9A	0.6096	0.3521	0.7373	0.091*
H9B	0.5794	0.2016	0.6761	0.091*
H9C	0.5100	0.3643	0.6666	0.091*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl	0.0696 (4)	0.0753 (4)	0.0577 (4)	−0.0114 (3)	−0.0042 (3)	−0.0050 (2)
N	0.0434 (9)	0.0508 (9)	0.0522 (9)	−0.0023 (7)	0.0088 (7)	−0.0046 (7)
C1	0.0372 (9)	0.0385 (8)	0.0526 (10)	0.0041 (7)	0.0095 (7)	0.0015 (7)
O1	0.0522 (9)	0.0643 (9)	0.1197 (15)	−0.0190 (8)	0.0158 (9)	−0.0066 (9)
C2	0.0394 (9)	0.0423 (9)	0.0509 (10)	−0.0021 (7)	0.0100 (7)	0.0035 (7)
O2	0.0701 (10)	0.0856 (11)	0.0755 (12)	−0.0061 (8)	−0.0060 (8)	−0.0214 (9)
C3	0.0455 (10)	0.0446 (10)	0.0544 (11)	0.0033 (8)	0.0031 (8)	0.0022 (8)
C4	0.0631 (12)	0.0558 (12)	0.0481 (11)	0.0060 (9)	0.0143 (9)	0.0089 (8)
C5	0.0535 (11)	0.0511 (11)	0.0673 (13)	0.0018 (9)	0.0253 (9)	0.0131 (9)
C6	0.0384 (9)	0.0385 (9)	0.0690 (13)	0.0007 (7)	0.0126 (8)	0.0029 (8)
C7	0.0377 (10)	0.0444 (10)	0.0900 (16)	−0.0023 (8)	0.0098 (9)	−0.0042 (9)
C8	0.0433 (10)	0.0534 (11)	0.0715 (14)	0.0020 (8)	−0.0009 (9)	−0.0132 (9)
C9	0.0596 (12)	0.0710 (14)	0.0530 (12)	0.0004 (10)	0.0141 (9)	0.0037 (10)

Geometric parameters (Å, °)

Cl—C3	1.7361 (19)	C3—C4	1.396 (3)
N—C8	1.369 (2)	C4—C5	1.383 (3)
N—C1	1.397 (2)	C4—H4A	0.9300
N—C9	1.451 (3)	C5—C6	1.373 (3)
C1—C2	1.383 (2)	C5—H5A	0.9300
C1—C6	1.406 (2)	C6—C7	1.468 (3)
O1—C7	1.215 (2)	C7—C8	1.519 (3)
C2—C3	1.376 (3)	C9—H9A	0.9600
C2—H2A	0.9300	C9—H9B	0.9600
O2—C8	1.222 (3)	C9—H9C	0.9600
C8—N—C1	109.98 (16)	C4—C5—H5A	120.4
C8—N—C9	124.86 (18)	C5—C6—C1	120.85 (18)
C1—N—C9	125.16 (15)	C5—C6—C7	133.59 (17)
C2—C1—N	127.17 (16)	C1—C6—C7	105.55 (17)
C2—C1—C6	121.09 (17)	O1—C7—C6	128.9 (2)
N—C1—C6	111.74 (16)	O1—C7—C8	125.2 (2)
C3—C2—C1	116.40 (16)	C6—C7—C8	105.93 (16)
C3—C2—H2A	121.8	O2—C8—N	125.0 (2)
C1—C2—H2A	121.8	O2—C8—C7	128.2 (2)
C2—C3—C4	123.89 (18)	N—C8—C7	106.77 (17)
C2—C3—Cl	117.88 (14)	N—C9—H9A	109.5
C4—C3—Cl	118.23 (15)	N—C9—H9B	109.5
C5—C4—C3	118.50 (19)	H9A—C9—H9B	109.5
C5—C4—H4A	120.8	N—C9—H9C	109.5
C3—C4—H4A	120.8	H9A—C9—H9C	109.5
C6—C5—C4	119.24 (17)	H9B—C9—H9C	109.5
C6—C5—H5A	120.4
C8—N—C1—C2	179.45 (16)	C2—C1—C6—C7	179.49 (15)
C9—N—C1—C2	0.2 (3)	N—C1—C6—C7	−0.97 (19)
C8—N—C1—C6	0.0 (2)	C5—C6—C7—O1	2.2 (4)
C9—N—C1—C6	−179.27 (17)	C1—C6—C7—O1	−178.19 (19)
N—C1—C2—C3	−179.06 (16)	C5—C6—C7—C8	−178.04 (19)
C6—C1—C2—C3	0.4 (2)	C1—C6—C7—C8	1.52 (19)
C1—C2—C3—C4	1.0 (3)	C1—N—C8—O2	−179.21 (19)
C1—C2—C3—Cl	−178.72 (13)	C9—N—C8—O2	0.0 (3)
C2—C3—C4—C5	−1.9 (3)	C1—N—C8—C7	1.0 (2)
Cl—C3—C4—C5	177.82 (14)	C9—N—C8—C7	−179.76 (16)
C3—C4—C5—C6	1.3 (3)	O1—C7—C8—O2	−1.6 (3)
C4—C5—C6—C1	0.0 (3)	C6—C7—C8—O2	178.7 (2)
C4—C5—C6—C7	179.48 (19)	O1—C7—C8—N	178.14 (18)
C2—C1—C6—C5	−0.9 (3)	C6—C7—C8—N	−1.6 (2)
N—C1—C6—C5	178.65 (16)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1i	0.93	2.50	3.419 (2)	168
C9—H9A···O2	0.96	2.53	2.906 (3)	103

Symmetry codes: (i) x−1/2, y−1/2, z.