6-Chloro-1-methyl­indoline-2,3-dione

Liu, H.Q.; Tang, W.; Wang, D.C.; Ou-yang, P.K.

doi:10.1107/S1600536811051294

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o14

doi:10.1107/S1600536811051294

Open

access

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

Hua Quan Liu,^a Wei Tang,^a De Cai Wang ^a ^* and Ping Kai Ou-yang ^a

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

(Received 15 November 2011; accepted 29 November 2011; online 3 December 2011)

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, C 2/c
a = 13.077 (3) Å
b = 7.9390 (16) Å
c = 16.673 (3) Å
β = 101.95 (3)°
V = 1693.5 (6) Å³
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[F² > 2σ(F²)] = 0.040
wR(F²) = 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

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) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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/S1600536811051294/pv2487sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051294/pv2487Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051294/pv2487Isup3.cml

checkCIF report

Comment top

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).

Related literature top

The title compound is a halogenated derivative of isatin. For the cytotoxic and antineoplastic activity of halogenated derivatives of isatin, 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 top

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.

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. The intermolecular hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₉H₆ClNO₂	F(000) = 800
M_r = 195.60	D_x = 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 top

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

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.080P)²] where P = (F_o² + 2F_c²)/3
1557 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.17 e Å⁻³
1 restraint	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₆ClNO₂	V = 1693.5 (6) Å³
M_r = 195.60	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.077 (3) Å	µ = 0.41 mm⁻¹
b = 7.9390 (16) Å	T = 293 K
c = 16.673 (3) Å	0.30 × 0.20 × 0.10 mm
β = 101.95 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1250 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.031
T_min = 0.887, T_max = 0.960	3 standard reflections every 200 reflections
3124 measured reflections	intensity decay: 1%
1557 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.118	H-atom parameters constrained
S = 1.00	Δρ_max = 0.17 e Å⁻³
1557 reflections	Δρ_min = −0.27 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	0.44670 (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 (Å²) top

	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, º) top

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, º) top

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 code: (i) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₆ClNO₂
M_r	195.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	13.077 (3), 7.9390 (16), 16.673 (3)
β (°)	101.95 (3)
V (Å³)	1693.5 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.887, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	3124, 1557, 1250
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 1.00
No. of reflections	1557
No. of parameters	119
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.27

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	2.50	3.419 (2)	168

Symmetry code: (i) x−1/2, y−1/2, z.

Acknowledgements

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

References

Bouhfid, R., Joly, N., Massoui, M., Cecchelli, R., Lequart, V., Martin, P. & Essassi, E. M. (2005). Heterocycles, 65, 2949–2955. CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Matesic, L., Locke, J. M., Bremner, J. B., Pyne, S. G., Skropeta, D., Ranson, M. & Vine, K. L. (2008). Bioorg. Med. Chem. 16, 3118–3124. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vine, K. L., Locke, J. M., Ranson, M., Pyne, S. G. & Bremner, J. B. (2007). Bioorg. Med. Chem. 15, 931–938. Web of Science CrossRef PubMed CAS Google Scholar
Wu, W., Zheng, T., Cao, S. & Xiao, Z. (2011). Acta Cryst. E67, o246. Web of Science CSD CrossRef IUCr Journals Google Scholar