4-Chloro-1-methyl­indoline-2,3-dione

Yu, J.G.; Tang, W.; Wang, D.C.; Xu, H.

doi:10.1107/S1600536811054171

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o219

doi:10.1107/S1600536811054171

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

Jian Guang Yu,^a Wei Tang,^a De Cai Wang ^a ^* and Hong Xu ^b

^aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Materials-Oriented Chemical Engineering, College of Food Science and Light Industry, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: dc_wang@hotmail.com

(Received 5 December 2011; accepted 16 December 2011; online 23 December 2011)

The title molecule, C₉H₆ClNO₂, is essentially planar; the maximum deviation of the indoline ring system is 0.027 (3) Å and the substituents do not deviate by more than 0.075 (2) Å from this plane. Intermolecular C—H⋯O hydrogen bonds consolidate the crystal structure.

Related literature

For the preparation of the title compound, see: Bouhfid et al. (2005 ). For a related crystal structure and background to isatin derivatives, see: Liu et al. (2011 ).

Experimental

Crystal data

C₉H₆ClNO₂
M_r = 195.60
Monoclinic, P 2₁ /c
a = 7.4890 (15) Å
b = 14.825 (3) Å
c = 7.3140 (15) Å
β = 90.27 (3)°
V = 812.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.919, T_max = 0.958
1607 measured reflections
1485 independent reflections
965 reflections with I > 2σ(I)
R_int = 0.042
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.155
S = 1.00
1485 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.58	3.323 (5)	137
C3—H3A⋯O2ⁱ	0.93	2.50	3.424 (5)	170
C9—H9A⋯O2ⁱⁱ	0.96	2.60	3.198 (5)	121
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811054171/pv2493sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054171/pv2493Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054171/pv2493Isup3.cml

checkCIF report

Comment top

As a part of our studies on the synthesis and structures of isatin derivatives (Liu et al., 2011), the title compound was synthesized and its structure is now reported in this article

The title molecule (Fig. 1) is essentially planar with the maximum deviation of C7 atom from the mean plane of the indoline ring (C1—C5/N/C6—C8) is 0.027 (3) A°. The substituents do not deviate more than 0.075 (2) Å from this plane. In the crystal structure, intermolecular and intramolecular C—H···O hydrogen bonds consolidate the crystal packing (Fig. 2 & Tab. 1).

Related literature top

For the preparation of the title compound, see: Bouhfid et al. (2005). For a related crystal structure and background to isatin derivatives, see: Liu et al. (2011).

Experimental top

The title compound was synthesized according to a reported procedure (Bouhfid et al.2005). 4-Chloroisatin (1.81 g, 0.01 mol) was reacted with iodomethane (2.84 g, 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. 464–467 K; yield 73%). Yellow crystals of the title compound were obtained by slow evaporation from ethanol at room temperature.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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).

Figures top

	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. Intermolecular hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₉H₆ClNO₂	F(000) = 400
M_r = 195.60	D_x = 1.600 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.4890 (15) Å	θ = 9–12°
b = 14.825 (3) Å	µ = 0.43 mm⁻¹
c = 7.3140 (15) Å	T = 293 K
β = 90.27 (3)°	Block, yellow
V = 812.0 (3) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	965 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 25.5°, θ_min = 2.7°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→17
T_min = 0.919, T_max = 0.958	l = 0→8
1607 measured reflections	3 standard reflections every 200 reflections
1485 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1485 reflections	Δρ_max = 0.28 e Å⁻³
119 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (4)

Crystal data top

C₉H₆ClNO₂	V = 812.0 (3) Å³
M_r = 195.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4890 (15) Å	µ = 0.43 mm⁻¹
b = 14.825 (3) Å	T = 293 K
c = 7.3140 (15) Å	0.20 × 0.10 × 0.10 mm
β = 90.27 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	965 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.919, T_max = 0.958	3 standard reflections every 200 reflections
1607 measured reflections	intensity decay: 1%
1485 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.00	Δρ_max = 0.28 e Å⁻³
1485 reflections	Δρ_min = −0.28 e Å⁻³
119 parameters

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

	x	y	z	U_iso*/U_eq
Cl	0.19910 (14)	0.55890 (7)	0.16100 (16)	0.0561 (4)
N	0.3254 (4)	0.88873 (19)	0.2061 (4)	0.0430 (8)
O1	0.6058 (4)	0.87503 (19)	0.3282 (5)	0.0676 (10)
C1	0.1324 (5)	0.6685 (2)	0.1324 (5)	0.0425 (9)
O2	0.5204 (4)	0.68317 (18)	0.3142 (4)	0.0606 (9)
C2	−0.0323 (5)	0.6886 (3)	0.0589 (5)	0.0490 (11)
H2A	−0.1085	0.6423	0.0230	0.059*
C3	−0.0848 (5)	0.7773 (3)	0.0381 (6)	0.0540 (12)
H3A	−0.1982	0.7897	−0.0078	0.065*
C4	0.0265 (5)	0.8479 (3)	0.0835 (6)	0.0484 (10)
H4A	−0.0097	0.9074	0.0677	0.058*
C5	0.1921 (5)	0.8279 (2)	0.1525 (5)	0.0375 (9)
C6	0.4690 (5)	0.8435 (3)	0.2721 (6)	0.0470 (10)
C7	0.4229 (5)	0.7422 (2)	0.2603 (5)	0.0412 (9)
C8	0.2447 (4)	0.7390 (2)	0.1784 (5)	0.0370 (9)
C9	0.3123 (5)	0.9847 (3)	0.1887 (7)	0.0587 (12)
H9A	0.4200	1.0121	0.2338	0.088*
H9B	0.2126	1.0060	0.2584	0.088*
H9C	0.2957	1.0003	0.0624	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0597 (7)	0.0389 (6)	0.0696 (8)	−0.0050 (5)	−0.0120 (5)	−0.0014 (5)
N	0.0351 (18)	0.0338 (17)	0.060 (2)	0.0011 (14)	−0.0083 (15)	−0.0031 (16)
O1	0.0420 (17)	0.0512 (18)	0.109 (3)	−0.0072 (14)	−0.0290 (17)	−0.0120 (18)
C1	0.043 (2)	0.042 (2)	0.043 (2)	−0.0048 (17)	−0.0040 (18)	−0.0005 (18)
O2	0.0446 (17)	0.0455 (17)	0.092 (2)	0.0107 (13)	−0.0241 (16)	−0.0012 (16)
C2	0.036 (2)	0.063 (3)	0.048 (2)	−0.016 (2)	−0.0084 (19)	−0.003 (2)
C3	0.034 (2)	0.077 (3)	0.051 (2)	0.000 (2)	−0.0105 (19)	0.006 (2)
C4	0.036 (2)	0.056 (2)	0.052 (2)	0.0071 (19)	−0.0058 (18)	0.006 (2)
C5	0.033 (2)	0.039 (2)	0.041 (2)	0.0036 (16)	−0.0057 (16)	−0.0009 (17)
C6	0.033 (2)	0.043 (2)	0.065 (3)	0.0051 (18)	−0.0069 (19)	−0.005 (2)
C7	0.034 (2)	0.037 (2)	0.052 (2)	0.0065 (17)	−0.0039 (18)	−0.0021 (19)
C8	0.0305 (19)	0.035 (2)	0.045 (2)	0.0036 (15)	−0.0068 (17)	−0.0031 (17)
C9	0.057 (3)	0.035 (2)	0.083 (3)	0.002 (2)	−0.006 (2)	0.001 (2)

Geometric parameters (Å, º) top

Cl—C1	1.712 (4)	C3—C4	1.378 (6)
N—C6	1.354 (5)	C3—H3A	0.9300
N—C5	1.400 (4)	C4—C5	1.369 (5)
N—C9	1.431 (5)	C4—H4A	0.9300
O1—C6	1.197 (4)	C5—C8	1.389 (5)
C1—C2	1.376 (5)	C6—C7	1.544 (5)
C1—C8	1.382 (5)	C7—C8	1.461 (5)
O2—C7	1.204 (4)	C9—H9A	0.9600
C2—C3	1.381 (6)	C9—H9B	0.9600
C2—H2A	0.9300	C9—H9C	0.9600

C6—N—C5	110.2 (3)	C8—C5—N	111.8 (3)
C6—N—C9	125.2 (3)	O1—C6—N	127.3 (4)
C5—N—C9	124.6 (3)	O1—C6—C7	126.1 (4)
C2—C1—C8	118.3 (4)	N—C6—C7	106.6 (3)
C2—C1—Cl	120.9 (3)	O2—C7—C8	131.4 (4)
C8—C1—Cl	120.7 (3)	O2—C7—C6	123.6 (3)
C1—C2—C3	120.2 (4)	C8—C7—C6	104.9 (3)
C1—C2—H2A	119.9	C1—C8—C5	120.8 (3)
C3—C2—H2A	119.9	C1—C8—C7	132.7 (3)
C4—C3—C2	121.7 (4)	C5—C8—C7	106.5 (3)
C4—C3—H3A	119.2	N—C9—H9A	109.5
C2—C3—H3A	119.2	N—C9—H9B	109.5
C5—C4—C3	118.0 (4)	H9A—C9—H9B	109.5
C5—C4—H4A	121.0	N—C9—H9C	109.5
C3—C4—H4A	121.0	H9A—C9—H9C	109.5
C4—C5—C8	120.8 (4)	H9B—C9—H9C	109.5
C4—C5—N	127.4 (4)

C8—C1—C2—C3	−2.2 (6)	N—C6—C7—O2	−177.4 (4)
Cl—C1—C2—C3	179.5 (3)	O1—C6—C7—C8	−178.4 (4)
C1—C2—C3—C4	2.3 (6)	N—C6—C7—C8	1.3 (4)
C2—C3—C4—C5	−0.7 (6)	C2—C1—C8—C5	0.6 (6)
C3—C4—C5—C8	−1.0 (6)	Cl—C1—C8—C5	178.9 (3)
C3—C4—C5—N	179.6 (4)	C2—C1—C8—C7	178.7 (4)
C6—N—C5—C4	178.3 (4)	Cl—C1—C8—C7	−3.0 (6)
C9—N—C5—C4	−3.1 (6)	C4—C5—C8—C1	1.0 (6)
C6—N—C5—C8	−1.1 (5)	N—C5—C8—C1	−179.5 (3)
C9—N—C5—C8	177.4 (4)	C4—C5—C8—C7	−177.5 (4)
C5—N—C6—O1	179.5 (4)	N—C5—C8—C7	1.9 (4)
C9—N—C6—O1	0.9 (7)	O2—C7—C8—C1	−1.7 (8)
C5—N—C6—C7	−0.2 (4)	C6—C7—C8—C1	179.8 (4)
C9—N—C6—C7	−178.7 (4)	O2—C7—C8—C5	176.6 (4)
O1—C6—C7—O2	3.0 (7)	C6—C7—C8—C5	−1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.93	2.58	3.323 (5)	137
C3—H3A···O2ⁱ	0.93	2.50	3.424 (5)	170
C9—H9A···O1	0.96	2.56	2.915 (5)	102
C9—H9A···O2ⁱⁱ	0.96	2.60	3.198 (5)	121

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₆ClNO₂
M_r	195.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4890 (15), 14.825 (3), 7.3140 (15)
β (°)	90.27 (3)
V (Å³)	812.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.919, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	1607, 1485, 965
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.155, 1.00
No. of reflections	1485
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.28

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.93	2.58	3.323 (5)	137
C3—H3A···O2ⁱ	0.93	2.50	3.424 (5)	170
C9—H9A···O1	0.96	2.56	2.915 (5)	102
C9—H9A···O2ⁱⁱ	0.96	2.60	3.198 (5)	121

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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