5-Bromo-1-methyl­indolin-2-one

Yuan, M.-S.; Shuai, Q.; Wang, L.; Li, X.-Z.; Yu, R.-J.

doi:10.1107/S1600536809021564

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1553

doi:10.1107/S1600536809021564

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5-Bromo-1-methylindolin-2-one

Mao-Sen Yuan,^a ^* Qi Shuai,^a Lin Wang,^a Xiao-Zhou Li ^a and Rui-Jin Yu ^a

^aCollege of Science, Northwest A&F University, Yangling 712100, Shanxi Province, People's Republic of China
^*Correspondence e-mail: yuanms@nwsuaf.edu.cn

(Received 25 May 2009; accepted 6 June 2009; online 13 June 2009)

The title molecule, C₉H₈BrNO, approximates a full planar conformation. The interplanar angle between the benzene and five-membered rings of the indoline system is 1.38 (1)°. There is an obvious π-delocalization involving the N—C=O group in the five-membered ring, which is greater than that involving the N—C C(benzene) group.

Related literature

For the biological activity of indole-2-one derivatives, see: Frohner et al. (2005 ); Xie et al. (2007 ). For a related structure, see: Lipkowski et al. (1995 ).

Experimental

Crystal data

C₉H₈BrNO
M_r = 226.07
Monoclinic, P 2₁ /c
a = 10.5134 (4) Å
b = 11.0926 (4) Å
c = 7.7168 (3) Å
β = 103.229 (2)°
V = 876.06 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.64 mm⁻¹
T = 293 K
0.47 × 0.45 × 0.44 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.122, T_max = 0.130
6684 measured reflections
2012 independent reflections
1655 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 1.06
2012 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021564/bh2231sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021564/bh2231Isup2.hkl

checkCIF report

Comment top

Indole-2-one derivatives have been widely explored due to their wide range of biological activities (Frohner et al., 2005; Xie et al., 2007). Indole-2-one may also be used as a precuesor for synthesizing organic lighting compounds because of its perfect planar conformation. In the course of exploring new luminescent compounds, we obtained an intermediate compound 5-bromo-1-methylindolin-2-one (I). Here we report the structure and synthesis of (I).

The molecule lies approximately in a plane (Fig. 1). The interplanar angle between the benzene group and the five-membered ring is 1.38 (1)° and the maximum displacement from the least-squares plane defined by all the 9 atoms of the indoline framework is 0.057 (3) Å for atom C9. The alternating long and short bond lengths are observed in the benzene ring: C1—C2 = 1.386 (3), C2—C3 = 1.370 (3), C3—C4 = 1.398 (3), C4—C5 = 1.377 (3), C5—C6 = 1.393 (3), C1—C6 = 1.375 (4) Å. The difference among the three C—N bond lengths is obvious, C4—N1 = 1.394 (3), C8—N1 = 1.376 (3), C9—N1 = 1.451 (3) Å, and indicates the presence of an appropriate π delocalization involving the C8—N1 and C8—O1 bonds. The structural conformation of the title molecule (I) is similar to that of 1-methylindolin-2-one (Lipkowski et al., 1995).

The molecules are packed in P2₁/c space group which is different from that of 1-methylindolin-2-one (Pbca). There are no classic hydrogen bonds in this structure. However, the weak intermolecular interaction C7—H7B···O1 (2 - x, -y, 1 - z), is helpful to the stabilization of the packing (Fig. 2). This intermolecular hydrogen bond is characterized by the bond lengths of 0.97 (C7—H7B) and 2.51 Å (H7B···O1).

Related literature top

For the biological activity of indole-2-one derivatives, see: Frohner et al. (2005); Xie et al. (2007). For a related structure, see: Lipkowski et al. (1995)

Experimental top

1-Methylindolin-2-one (0.50 g) was dissolved in acetonitrile (10 ml). After cooling the mixture to 263 K, an acetonitrile solution of NBS (0.60 g) was slowly added. After stirring for 24 h., the mixture was poured into ice water and further stirred for 1 h. The solution was extracted with chloroform and dried over Na₂SO₄. After removing the solvent, the crude product was purified by recrystallization from ethanol, affording the title compound, (I) (0.58 g, 76%). Then the compound (I) was dissolved in a mixture of solvents, dichloromethane and isopropyl ether, and pink block crystals were formed on slow evaporation at room temperature over one week.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A a axis view of the molecular packing of (I).

5-Bromo-1-methylindolin-2-one top

Crystal data top

C₉H₈BrNO	F(000) = 448
M_r = 226.07	D_x = 1.714 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2899 reflections
a = 10.5134 (4) Å	θ = 2.7–27.5°
b = 11.0926 (4) Å	µ = 4.64 mm⁻¹
c = 7.7168 (3) Å	T = 293 K
β = 103.229 (2)°	Block, pink
V = 876.06 (6) Å³	0.47 × 0.45 × 0.44 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2012 independent reflections
Radiation source: fine-focus sealed tube	1655 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→10
T_min = 0.122, T_max = 0.130	k = −11→14
6684 measured reflections	l = −10→10

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.071	w = 1/[σ²(F_o²) + (0.03P)² + 0.5204P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2012 reflections	Δρ_max = 0.37 e Å⁻³
111 parameters	Δρ_min = −0.49 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0099 (11)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₉H₈BrNO	V = 876.06 (6) Å³
M_r = 226.07	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5134 (4) Å	µ = 4.64 mm⁻¹
b = 11.0926 (4) Å	T = 293 K
c = 7.7168 (3) Å	0.47 × 0.45 × 0.44 mm
β = 103.229 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2012 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1655 reflections with I > 2σ(I)
T_min = 0.122, T_max = 0.130	R_int = 0.022
6684 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.06	Δρ_max = 0.37 e Å⁻³
2012 reflections	Δρ_min = −0.49 e Å⁻³
111 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.28547 (2)	0.07936 (3)	0.20946 (4)	0.04945 (13)
C1	0.4602 (2)	0.0991 (2)	0.1860 (3)	0.0355 (5)
C2	0.5537 (2)	0.0170 (2)	0.2694 (3)	0.0374 (5)
H2	0.5316	−0.0460	0.3366	0.045*
C3	0.6793 (2)	0.0308 (2)	0.2506 (3)	0.0329 (5)
C4	0.7111 (2)	0.1265 (2)	0.1505 (3)	0.0316 (5)
C5	0.6183 (2)	0.2080 (2)	0.0666 (3)	0.0400 (6)
H5	0.6401	0.2710	−0.0006	0.048*
C6	0.4907 (2)	0.1926 (2)	0.0858 (3)	0.0399 (6)
H6	0.4258	0.2460	0.0306	0.048*
C7	0.8012 (3)	−0.0418 (2)	0.3173 (4)	0.0435 (6)
H7A	0.7903	−0.1238	0.2725	0.052*
H7B	0.8244	−0.0438	0.4464	0.052*
C8	0.9037 (2)	0.0246 (2)	0.2444 (3)	0.0404 (6)
C9	0.9086 (3)	0.2039 (3)	0.0514 (4)	0.0537 (7)
H9A	0.9993	0.1827	0.0715	0.081*
H9B	0.9006	0.2850	0.0908	0.081*
H9C	0.8688	0.1978	−0.0733	0.081*
N1	0.84354 (19)	0.12225 (19)	0.1502 (3)	0.0360 (4)
O1	1.01834 (18)	−0.0009 (2)	0.2635 (3)	0.0580 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03020 (16)	0.0645 (2)	0.05570 (18)	−0.00283 (13)	0.01405 (11)	−0.01295 (13)
C1	0.0260 (11)	0.0432 (15)	0.0375 (11)	−0.0013 (10)	0.0077 (9)	−0.0084 (10)
C2	0.0390 (13)	0.0348 (13)	0.0409 (12)	−0.0030 (11)	0.0142 (10)	0.0002 (10)
C3	0.0326 (12)	0.0315 (12)	0.0343 (11)	−0.0007 (10)	0.0068 (9)	−0.0015 (9)
C4	0.0315 (12)	0.0321 (12)	0.0313 (11)	−0.0028 (10)	0.0076 (9)	−0.0044 (9)
C5	0.0439 (14)	0.0339 (14)	0.0441 (13)	−0.0008 (11)	0.0136 (11)	0.0049 (10)
C6	0.0354 (13)	0.0387 (14)	0.0425 (13)	0.0073 (11)	0.0027 (10)	−0.0004 (11)
C7	0.0353 (14)	0.0452 (15)	0.0499 (14)	0.0056 (11)	0.0098 (11)	0.0097 (12)
C8	0.0338 (14)	0.0463 (15)	0.0415 (13)	0.0003 (11)	0.0093 (10)	−0.0034 (11)
C9	0.0457 (16)	0.0552 (18)	0.0667 (18)	−0.0071 (13)	0.0263 (14)	0.0092 (14)
N1	0.0329 (11)	0.0388 (11)	0.0382 (10)	−0.0035 (9)	0.0121 (8)	0.0001 (9)
O1	0.0322 (11)	0.0747 (15)	0.0686 (12)	0.0084 (10)	0.0147 (9)	0.0060 (11)

Geometric parameters (Å, º) top

Br1—C1	1.900 (2)	C6—H6	0.9300
C1—C6	1.375 (4)	C7—C8	1.515 (4)
C1—C2	1.386 (3)	C7—H7A	0.9700
C2—C3	1.370 (3)	C7—H7B	0.9700
C2—H2	0.9300	C8—O1	1.214 (3)
C3—C4	1.398 (3)	C8—N1	1.376 (3)
C3—C7	1.502 (3)	C9—N1	1.451 (3)
C4—C5	1.377 (3)	C9—H9A	0.9600
C4—N1	1.394 (3)	C9—H9B	0.9600
C5—C6	1.393 (3)	C9—H9C	0.9600
C5—H5	0.9300

C6—C1—C2	121.7 (2)	C3—C7—C8	103.6 (2)
C6—C1—Br1	119.70 (18)	C3—C7—H7A	111.0
C2—C1—Br1	118.56 (18)	C8—C7—H7A	111.0
C3—C2—C1	118.4 (2)	C3—C7—H7B	111.0
C3—C2—H2	120.8	C8—C7—H7B	111.0
C1—C2—H2	120.8	H7A—C7—H7B	109.0
C2—C3—C4	120.1 (2)	O1—C8—N1	124.9 (2)
C2—C3—C7	132.2 (2)	O1—C8—C7	127.8 (3)
C4—C3—C7	107.7 (2)	N1—C8—C7	107.4 (2)
C5—C4—N1	128.4 (2)	N1—C9—H9A	109.5
C5—C4—C3	121.7 (2)	N1—C9—H9B	109.5
N1—C4—C3	109.9 (2)	H9A—C9—H9B	109.5
C4—C5—C6	117.7 (2)	N1—C9—H9C	109.5
C4—C5—H5	121.1	H9A—C9—H9C	109.5
C6—C5—H5	121.1	H9B—C9—H9C	109.5
C1—C6—C5	120.4 (2)	C8—N1—C4	111.38 (19)
C1—C6—H6	119.8	C8—N1—C9	123.7 (2)
C5—C6—H6	119.8	C4—N1—C9	124.8 (2)

C6—C1—C2—C3	0.1 (4)	C2—C3—C7—C8	179.2 (3)
Br1—C1—C2—C3	179.31 (18)	C4—C3—C7—C8	0.4 (3)
C1—C2—C3—C4	0.6 (3)	C3—C7—C8—O1	−179.9 (3)
C1—C2—C3—C7	−178.2 (2)	C3—C7—C8—N1	0.4 (3)
C2—C3—C4—C5	−0.9 (4)	O1—C8—N1—C4	179.3 (2)
C7—C3—C4—C5	178.1 (2)	C7—C8—N1—C4	−1.0 (3)
C2—C3—C4—N1	180.0 (2)	O1—C8—N1—C9	4.0 (4)
C7—C3—C4—N1	−1.0 (3)	C7—C8—N1—C9	−176.2 (2)
N1—C4—C5—C6	179.5 (2)	C5—C4—N1—C8	−177.7 (2)
C3—C4—C5—C6	0.5 (3)	C3—C4—N1—C8	1.3 (3)
C2—C1—C6—C5	−0.5 (4)	C5—C4—N1—C9	−2.6 (4)
Br1—C1—C6—C5	−179.67 (18)	C3—C4—N1—C9	176.5 (2)
C4—C5—C6—C1	0.2 (4)

Experimental details

Crystal data
Chemical formula	C₉H₈BrNO
M_r	226.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.5134 (4), 11.0926 (4), 7.7168 (3)
β (°)	103.229 (2)
V (Å³)	876.06 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.64
Crystal size (mm)	0.47 × 0.45 × 0.44

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.122, 0.130
No. of measured, independent and observed [I > 2σ(I)] reflections	6684, 2012, 1655
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.06
No. of reflections	2012
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.49

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

C3—C4	1.398 (3)	C8—O1	1.214 (3)
C4—N1	1.394 (3)	C8—N1	1.376 (3)

Acknowledgements

This work was supported by the Scientific Research Foundation of Northwest A&F University (grant No. 2111020828).

References

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