1-(2,6-Dichloro­phen­yl)indolin-2-one

Hanif, M.; Rafiq, M.; Saleem, M.; Qadeer, G.; Wong, W.-Y.

doi:10.1107/S1600536809005807

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o583

doi:10.1107/S1600536809005807

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1-(2,6-Dichlorophenyl)indolin-2-one

Muhammad Hanif,^a Muhammad Rafiq,^a Muhammad Saleem,^b Ghulam Qadeer ^a ^* and Wai-Yeung Wong ^c ‡

^aDepartment of Chemistry, Quaid-i-Azam Univeristy, Islamabad 45320, Pakistan, ^bDepartment of Chemistry, University of Sargodah, Sargodah, Pakistan, and ^cDepartment of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, People's Republic of China
^*Correspondence e-mail: qadeerqau@yahoo.com

(Received 15 February 2009; accepted 18 February 2009; online 25 February 2009)

In the molecule of the title compound, C₁₄H₉Cl₂NO, the planar indole ring system [with a maximum deviation of 0.020 (2) Å for the N atom] is oriented at a dihedral angle of 72.17 (3)° with respect to the phenyl ring. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules. A weak C—H⋯π interaction may further stabilize the structure.

Related literature

For general background, see: Hibino & Choshi (2002 ); Somei & Yamada (2003 ); Popp (1977 , 1984 ). For related structures, see: Chakraborty & Talapatra (1985 ); Chakraborty et al. (1985 ); De (1992 ); De & Kitagawa (1991a ,b ); Itai et al. (1978 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₉Cl₂NO
M_r = 278.12
Monoclinic, P 2₁
a = 7.1412 (8) Å
b = 8.0241 (9) Å
c = 11.0510 (13) Å
β = 105.789 (2)°
V = 609.35 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 173 K
0.30 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.755, T_max = 0.902
3710 measured reflections
2328 independent reflections
2295 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.060
S = 1.06
2328 reflections
163 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 705 Friedel pairs
Flack parameter: −0.02 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1ⁱ	0.95	2.55	3.2267 (19)	128
C8—H8A⋯Cg1ⁱⁱ	0.99	2.74	3.6125 (23)	147
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ . Cg1 is the centroid of the C9–C14 ring.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005807/hk2625sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005807/hk2625Isup2.hkl

checkCIF report

Comment top

Indolinones are a class of heterocyclic compounds found in many natural products and in a number of marketed drugs (Hibino & Choshi, 2002; Somei & Yamada, 2003). They have diverse chemical structures and complex physiological and pharmacological actions. The search for potential drugs and their mechanism of action has been difficult because of their complexity. These compounds contain both oxoindole and dioxolane moieties which have independently been seen in other anticonvulsants (Popp, 1977, 1984). The title compound, a chloro analogue, was found to be most potent in the MES test. Since no common target site has yet been established, X-ray analysis was undertaken to search its crystal structure, which may help to understand the mechanism of action at the molecular level.

In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (N1/C7-C10) and C (C9-C14) are, of course, planar and the dihedral angles between them are A/B = 71.73 (3)°, A/C = 72.43 (3)° and B/C = 1.07 (3)°. So, rings B and C are nearly coplanar. Ring A is oriented with respect to the planar indole ring system at a dihedral angle of 72.17 (3)°. The C8-C9 [1.4955 (19) Å] bond length may be compared with the corresponding values in other indoline nuclei (Itai et al., 1978; Chakraborty & Talapatra, 1985; Chakraborty et al., 1985; De & Kitagawa, 1991a,b; De, 1992).

In the crystal structure, weak intermolecular C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The weak C—H···π interaction (Table 1) may further stabilize the structure.

Related literature top

For general background, see: Hibino & Choshi (2002); Somei & Yamada (2003); Popp (1977); Popp (1984). For related structures, see: Chakraborty & Talapatra (1985); Chakraborty et al. (1985); De (1992); De & Kitagawa (1991a,b); Itai et al. (1978). For bond-length data, see: Allen et al. (1987). Cg1 is the centroid of the C9–C14 ring.

Experimental top

For the preparation of the title compound, sodium salt of 2-(2-(2,6-dichloro- phenylamino)phenyl)acetate (3.18 g, 10 mmol) was dissolved in distilled water (50 ml) and heated on a hot plate, until a homogeneous solution obtained, and then filtered to remove the undissolved product. It was poured into concentrated hydrochloric acid (5 ml) diluted with ice water (25 ml) in an Erlenmeyer flask to obtain 2-(2-(2,6-dichlorophenylamino)phenyl)acetic acid. Then, it was stand for 15 min in an ice bath. The crude product was separated and recrystallized in ethanol. 2-(2-(2,6-dichlorophenylamino)phenyl)acetic acid (2.96 g, 10 mmol) was refluxed in methanol (50 ml) in catalytic amount of sulfuric acid. As soon as a methyl ester is formed, it is cyclized to form the title compound, which was recrystallized in ethanol (yield; 79%; m.p. 420-421 K).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
	Fig. 3. The formation of the title compound.

1-(2,6-Dichlorophenyl)indolin-2-one top

Crystal data top

C₁₄H₉Cl₂NO	F(000) = 284
M_r = 278.12	D_x = 1.516 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2148 reflections
a = 7.1412 (8) Å	θ = 5.2–24.3°
b = 8.0241 (9) Å	µ = 0.52 mm⁻¹
c = 11.0510 (13) Å	T = 173 K
β = 105.789 (2)°	Block, yellow
V = 609.35 (12) Å³	0.30 × 0.24 × 0.20 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2328 independent reflections
Radiation source: fine-focus sealed tube	2295 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω and ϕ scans	θ_max = 28.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.755, T_max = 0.902	k = −9→10
3710 measured reflections	l = −14→11

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0379P)² + 0.0681P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2328 reflections	Δρ_max = 0.19 e Å⁻³
163 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 705 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (4)

Crystal data top

C₁₄H₉Cl₂NO	V = 609.35 (12) Å³
M_r = 278.12	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.1412 (8) Å	µ = 0.52 mm⁻¹
b = 8.0241 (9) Å	T = 173 K
c = 11.0510 (13) Å	0.30 × 0.24 × 0.20 mm
β = 105.789 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2328 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2295 reflections with I > 2σ(I)
T_min = 0.755, T_max = 0.902	R_int = 0.014
3710 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.060	Δρ_max = 0.19 e Å⁻³
S = 1.06	Δρ_min = −0.16 e Å⁻³
2328 reflections	Absolute structure: Flack (1983), 705 Friedel pairs
163 parameters	Absolute structure parameter: −0.02 (4)
1 restraint

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
Cl1	0.57381 (5)	0.76042 (5)	0.02255 (3)	0.03458 (10)
Cl2	0.05095 (6)	0.97960 (6)	0.25885 (3)	0.03843 (11)
O1	0.41005 (16)	0.54202 (14)	0.22865 (9)	0.0304 (2)
N1	0.43177 (17)	0.82839 (15)	0.24614 (10)	0.0230 (2)
C1	0.2984 (2)	0.86900 (18)	0.12903 (12)	0.0224 (2)
C2	0.3471 (2)	0.83882 (17)	0.01693 (12)	0.0243 (3)
C3	0.2172 (2)	0.8739 (2)	−0.09901 (13)	0.0302 (3)
H3A	0.2512	0.8509	−0.1747	0.036*
C4	0.0386 (2)	0.9425 (2)	−0.10285 (13)	0.0330 (3)
H4A	−0.0507	0.9663	−0.1819	0.040*
C5	−0.0126 (2)	0.9774 (2)	0.00703 (14)	0.0304 (3)
H5A	−0.1350	1.0266	0.0036	0.036*
C6	0.1176 (2)	0.93932 (19)	0.12198 (12)	0.0266 (3)
C7	0.48390 (19)	0.66561 (18)	0.28346 (12)	0.0233 (3)
C8	0.6499 (2)	0.67599 (18)	0.40391 (12)	0.0249 (3)
H8A	0.6135	0.6223	0.4749	0.030*
H8B	0.7688	0.6219	0.3929	0.030*
C9	0.6805 (2)	0.85913 (18)	0.42570 (12)	0.0234 (3)
C10	0.54970 (19)	0.94523 (17)	0.32861 (11)	0.0219 (2)
C11	0.5448 (2)	1.11669 (19)	0.32044 (13)	0.0286 (3)
H11A	0.4558	1.1731	0.2533	0.034*
C12	0.6774 (2)	1.2032 (2)	0.41607 (14)	0.0335 (3)
H12A	0.6783	1.3216	0.4138	0.040*
C13	0.8073 (2)	1.1219 (2)	0.51397 (15)	0.0357 (3)
H13A	0.8950	1.1846	0.5778	0.043*
C14	0.8101 (2)	0.9477 (2)	0.51951 (13)	0.0310 (3)
H14A	0.8994	0.8912	0.5865	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03021 (17)	0.0422 (2)	0.03333 (16)	0.00882 (15)	0.01213 (12)	−0.00025 (14)
Cl2	0.04088 (19)	0.0480 (2)	0.03094 (16)	0.01679 (17)	0.01741 (14)	0.00795 (15)
O1	0.0330 (5)	0.0230 (5)	0.0309 (5)	−0.0025 (4)	0.0011 (4)	−0.0026 (4)
N1	0.0249 (5)	0.0208 (5)	0.0204 (5)	0.0012 (4)	0.0010 (4)	−0.0009 (4)
C1	0.0235 (6)	0.0220 (6)	0.0197 (5)	0.0010 (5)	0.0025 (5)	0.0010 (4)
C2	0.0245 (6)	0.0223 (6)	0.0256 (6)	0.0011 (5)	0.0063 (5)	−0.0021 (5)
C3	0.0358 (8)	0.0322 (8)	0.0206 (6)	0.0009 (6)	0.0043 (5)	−0.0003 (5)
C4	0.0320 (7)	0.0379 (8)	0.0240 (6)	0.0021 (6)	−0.0012 (5)	0.0041 (6)
C5	0.0242 (6)	0.0343 (8)	0.0303 (6)	0.0058 (6)	0.0035 (5)	0.0062 (6)
C6	0.0274 (7)	0.0276 (7)	0.0251 (6)	0.0031 (6)	0.0077 (5)	0.0034 (5)
C7	0.0216 (6)	0.0239 (6)	0.0229 (5)	0.0004 (5)	0.0037 (5)	0.0007 (4)
C8	0.0235 (6)	0.0236 (6)	0.0241 (6)	0.0037 (5)	0.0006 (5)	0.0007 (5)
C9	0.0224 (6)	0.0244 (7)	0.0226 (5)	0.0010 (5)	0.0049 (5)	−0.0020 (5)
C10	0.0236 (6)	0.0225 (6)	0.0194 (5)	−0.0006 (5)	0.0055 (4)	−0.0032 (4)
C11	0.0352 (8)	0.0236 (7)	0.0290 (6)	0.0008 (6)	0.0122 (6)	0.0003 (5)
C12	0.0397 (8)	0.0230 (7)	0.0414 (7)	−0.0057 (6)	0.0173 (7)	−0.0081 (6)
C13	0.0303 (8)	0.0373 (8)	0.0389 (8)	−0.0068 (7)	0.0085 (6)	−0.0162 (6)
C14	0.0259 (7)	0.0371 (8)	0.0272 (6)	−0.0002 (6)	0.0023 (5)	−0.0080 (5)

Geometric parameters (Å, º) top

C1—C6	1.392 (2)	C8—C9	1.4955 (19)
C1—C2	1.3958 (18)	C8—H8A	0.9900
C1—N1	1.4203 (15)	C8—H8B	0.9900
C2—C3	1.3908 (19)	C9—C14	1.3834 (19)
C2—Cl1	1.7223 (14)	C9—C10	1.3984 (18)
C3—C4	1.379 (2)	C10—C11	1.379 (2)
C3—H3A	0.9500	C10—N1	1.4146 (16)
C4—C5	1.389 (2)	C11—C12	1.397 (2)
C4—H4A	0.9500	C11—H11A	0.9500
C5—C6	1.3890 (19)	C12—C13	1.382 (2)
C5—H5A	0.9500	C12—H12A	0.9500
C6—Cl2	1.7353 (14)	C13—C14	1.399 (2)
C7—O1	1.2061 (17)	C13—H13A	0.9500
C7—N1	1.3896 (18)	C14—H14A	0.9500
C7—C8	1.5250 (17)

C6—C1—C2	118.16 (12)	C9—C8—H8B	111.0
C6—C1—N1	121.73 (12)	C7—C8—H8B	111.0
C2—C1—N1	120.12 (12)	H8A—C8—H8B	109.0
C3—C2—C1	121.19 (13)	C14—C9—C10	119.49 (14)
C3—C2—Cl1	119.46 (11)	C14—C9—C8	131.59 (14)
C1—C2—Cl1	119.34 (10)	C10—C9—C8	108.91 (12)
C4—C3—C2	119.23 (13)	C11—C10—C9	122.89 (13)
C4—C3—H3A	120.4	C11—C10—N1	128.25 (13)
C2—C3—H3A	120.4	C9—C10—N1	108.86 (12)
C3—C4—C5	121.01 (13)	C10—C11—C12	116.53 (14)
C3—C4—H4A	119.5	C10—C11—H11A	121.7
C5—C4—H4A	119.5	C12—C11—H11A	121.7
C4—C5—C6	119.01 (14)	C13—C12—C11	121.99 (15)
C4—C5—H5A	120.5	C13—C12—H12A	119.0
C6—C5—H5A	120.5	C11—C12—H12A	119.0
C5—C6—C1	121.38 (12)	C12—C13—C14	120.31 (14)
C5—C6—Cl2	118.81 (11)	C12—C13—H13A	119.8
C1—C6—Cl2	119.81 (10)	C14—C13—H13A	119.8
O1—C7—N1	125.35 (11)	C9—C14—C13	118.77 (14)
O1—C7—C8	127.81 (13)	C9—C14—H14A	120.6
N1—C7—C8	106.83 (11)	C13—C14—H14A	120.6
C9—C8—C7	103.83 (11)	C7—N1—C10	111.54 (10)
C9—C8—H8A	111.0	C7—N1—C1	123.04 (11)
C7—C8—H8A	111.0	C10—N1—C1	124.68 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱ	0.95	2.55	3.2267 (19)	128
C8—H8A···Cg1ⁱⁱ	0.99	2.74	3.613 (2)	147

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉Cl₂NO
M_r	278.12
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	173
a, b, c (Å)	7.1412 (8), 8.0241 (9), 11.0510 (13)
β (°)	105.789 (2)
V (Å³)	609.35 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.30 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.755, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	3710, 2328, 2295
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.060, 1.06
No. of reflections	2328
No. of parameters	163
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16
Absolute structure	Flack (1983), 705 Friedel pairs
Absolute structure parameter	−0.02 (4)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱ	0.95	2.55	3.2267 (19)	128
C8—H8A···Cg1ⁱⁱ	0.99	2.74	3.6125 (23)	147

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

Footnotes

‡Additonal contact author, e-mail: rwywong@net3.hkbu.edu.hk.

Acknowledgements

The authors gratefully acknowledge the financial support of the Higher Education Commission, Islamabad, Pakistan.

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