5-Bromo-1-methyl­indoline-2,3-dione

Kharbach, Y.; Haoudi, A.; Capet, F.; Mazzah, A.; El Ammari, L.

doi:10.1107/S2414314616007926

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160792

doi:10.1107/S2414314616007926

Open

access

5-Bromo-1-methylindoline-2,3-dione

Yassine Kharbach,^a ^* Amal Haoudi,^a Frédéric Capet,^b Ahmed Mazzah ^c and Lahcen El Ammari ^d

^aLaboratoire de Chimie Organique Appliquée-Chimie Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fès, Morocco, ^bUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Université Lille 1, 59650 Villeneuve d'Ascq Cedex, France, ^cUSR 3290 Miniaturisation pour l'analyse, la synthèse et la protéomique, 59655 Villeneuve d'Ascq Cedex, Université Lille1, France, and ^dLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: kharbachy26@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 12 May 2016; accepted 14 May 2016; online 24 May 2016)

In the title compound, C₉H₆BrNO₂, the indoline ring system, the two ketone O atoms and the Br atom are nearly coplanar, with the largest deviation from the mean plane being −0.1025 (4) Å. In the crystal, molecules are linked by two weak C—H⋯O hydrogen bonds and π–π interactions [inter-centroid distance = 3.510 (2) Å], forming a three-dimensional structure.

Keywords: crystal structure; Indoline ring; hydrogen bonds; π–π interaction.

CCDC reference: 1479815

3D view (loading...)

Chemical scheme

Structure description

Isatin derivatives have a wide range of biological properties. They display moderate antimicrobial effects in a wide variety of preclinical antimicrobial models. Isatin also exhibits other biological activities, such as anticonvulsant, cytotoxic, antifungal etc. Isatin and its analogs are versatile substrates, which can be used for the synthesis of numerous heterocyclic compounds (Sridhar et al., 2001 ; Sridhar & Sreenivasulu, 2001 ; Sarangapani & Reddy, 1994 ; Varma et al., 2004 ; Pandeya et al., 1999 ; Aboul-Fadl et al., 2010 ). In our work, we are interested in developing a new 5-bromoisatin and continuing the research work of Qachchachi to explore other applications (Qachchachi et al., 2013 , 2014 ; Kharbach et al., 2016 ). The present paper reports the synthesis and crystal structure of 5-bromo-1-methylindoline-2,3-dione (see Scheme).

The title compound is built up from two fused five- and six-membered rings linked to two ketone O atoms, a Br atom and a methyl group, as shown in Fig. 1. Besides the methyl H atoms, all the atoms of the structure are almost coplanar, with a maximum deviation of −0.1025 (4) Å for the Br1 atom.

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

In the crystal, molecules are linked by two weak C—H⋯O hydrogen bonds (Table 1) and π–π interactions [inter-centroid distance = 3.510 (2) Å], forming a three-dimensional network as shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O2ⁱ	0.96	2.56	3.454 (5)	155
C9—H9C⋯O1ⁱⁱ	0.96	2.61	3.403 (5)	141
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Molecules of the title compound linked by C—H⋯O hydrogen bonds and π–π interactions, forming a three-dimensionnal network.

Synthesis and crystallization

A mixture of 5-bromoisatin (0.4 g, 1.76 mmol) and iodomethane (0.12 ml, 0.84 mmol) in DMF (25 ml) in the presence of a catalytic amount of tetra-n-butylammonium bromide (0.1 g, 0.4 mmol) and potassium carbonate (0.6 g, 4.4 mmol) was stirred for 48 h. The title compound was obtained in 69% yield (m.p. 446 K). The solid obtained was recrystallized from ethanol to afford the title compound as orange crystals suitable for the X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The reflections 011 and 002 were affected by the beam-stop and were removed during the refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₆BrNO₂
M_r	240.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.0634 (1), 11.9235 (3), 18.0978 (5)
β (°)	96.170 (2)
V (Å³)	871.76 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.68
Crystal size (mm)	0.57 × 0.22 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.452, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9696, 2022, 1606
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.102, 1.07
No. of reflections	2022
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.34
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1479815

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616007926/sj4033sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616007926/sj4033Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616007926/sj4033Isup3.cml

checkCIF report

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Experimental top

Structure description top

Isatin derivatives have a wide range of biological properties. They have display moderate antimicrobial effect in a wide variety of preclinical antimicrobial models. Isatin is also exerting other biological activities, such as anticonvulsant activity, cytotoxic activity, antifungal activity etc. Isatin and its analogs are versatile substrates, which can be used for the synthesis of numerous heterocyclic compounds (Sridhar et al., 2001; Sridhar & Sreenivasulu, 2001; Sarangapani & Reddy, 1994; Varma et al., 2004; Pandeya et al., 1999; Aboul-Fadl et al., 2010). In our work, we are interested in developing a new 5-bromoisatin and continuing Qachchachi research work to explore other applications (Qachchachi et al., 2013, 2014; Kharbach et al., 2016). The present paper reports the synthesis and crystal structure of 5-bromo-1-methylindoline-2,3-dione (see Scheme).

The title compound is built up from two fused five- and six-membered rings linked to two ketone atoms, a Br atom and to a methyl group, as shown in Fig. 1. Besides the methyl H atoms belonging, all atoms of the structure are almost coplanar, with a maximum deviation of -0.1025 (4) Å for the Br1 atom.

In the crystal, molecules are linked by two weak C—H···O hydrogen bonds (Table 1) and by π–π interactions [inter-centroid distance = 3.510 (2) Å], forming a three-dimensional network as shown in Fig. 2.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. Molecules of the title compound linked by C—H···O hydrogen bonds and π–π interactions, forming a three-dimensionnal network.

5-Bromo-1-methylindoline-2,3-dione top

Crystal data top

C₉H₆BrNO₂	F(000) = 472
M_r = 240.06	D_x = 1.829 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.0634 (1) Å	Cell parameters from 2022 reflections
b = 11.9235 (3) Å	θ = 3.4–27.9°
c = 18.0978 (5) Å	µ = 4.68 mm⁻¹
β = 96.170 (2)°	T = 296 K
V = 871.76 (4) Å³	Sheet, orange
Z = 4	0.57 × 0.22 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	1606 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.041
φ and ω scans	θ_max = 27.9°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.452, T_max = 0.746	k = −15→15
9696 measured reflections	l = −23→23
2022 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0386P)² + 0.9585P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.002
2022 reflections	Δρ_max = 0.55 e Å⁻³
119 parameters	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₉H₆BrNO₂	V = 871.76 (4) Å³
M_r = 240.06	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.0634 (1) Å	µ = 4.68 mm⁻¹
b = 11.9235 (3) Å	T = 296 K
c = 18.0978 (5) Å	0.57 × 0.22 × 0.03 mm
β = 96.170 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2022 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1606 reflections with I > 2σ(I)
T_min = 0.452, T_max = 0.746	R_int = 0.041
9696 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.07	Δρ_max = 0.55 e Å⁻³
2022 reflections	Δρ_min = −0.34 e Å⁻³
119 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
C1	0.8560 (9)	0.3090 (2)	0.90400 (19)	0.0403 (7)
C2	0.8118 (8)	0.2178 (3)	0.85539 (18)	0.0370 (7)
C3	0.9557 (8)	0.1155 (3)	0.87379 (19)	0.0421 (7)
H3	0.9308	0.0550	0.8413	0.050*
C4	1.1383 (8)	0.1065 (3)	0.9425 (2)	0.0436 (8)
H4	1.2377	0.0385	0.9565	0.052*
C5	1.1765 (8)	0.1971 (3)	0.99091 (19)	0.0409 (7)
C6	1.0369 (9)	0.3001 (3)	0.9723 (2)	0.0433 (8)
H6	1.0640	0.3608	1.0047	0.052*
C7	0.6624 (10)	0.4026 (3)	0.8673 (2)	0.0494 (8)
C8	0.5016 (10)	0.3540 (3)	0.7928 (2)	0.0484 (8)
C9	0.5091 (11)	0.1663 (3)	0.7309 (2)	0.0526 (9)
H9A	0.3644	0.2029	0.6929	0.079*
H9B	0.3959	0.1041	0.7504	0.079*
H9C	0.7023	0.1397	0.7101	0.079*
N1	0.6078 (7)	0.2458 (2)	0.79063 (16)	0.0424 (6)
O1	0.6250 (8)	0.4971 (2)	0.88782 (17)	0.0689 (8)
O2	0.3142 (8)	0.4020 (2)	0.74695 (17)	0.0685 (8)
Br1	1.41762 (10)	0.17426 (3)	1.08562 (2)	0.05405 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0440 (18)	0.0291 (15)	0.0493 (19)	−0.0038 (13)	0.0112 (15)	0.0013 (13)
C2	0.0377 (16)	0.0318 (15)	0.0431 (17)	−0.0029 (13)	0.0120 (14)	0.0021 (13)
C3	0.0481 (19)	0.0330 (16)	0.0465 (18)	0.0046 (14)	0.0117 (15)	−0.0030 (14)
C4	0.0449 (18)	0.0351 (17)	0.0526 (19)	0.0081 (13)	0.0134 (15)	0.0032 (15)
C5	0.0361 (17)	0.0450 (18)	0.0426 (17)	0.0005 (13)	0.0091 (14)	0.0010 (14)
C6	0.0465 (19)	0.0341 (16)	0.0504 (19)	−0.0047 (14)	0.0108 (16)	−0.0035 (14)
C7	0.061 (2)	0.0324 (17)	0.056 (2)	0.0008 (15)	0.0117 (18)	0.0074 (15)
C8	0.056 (2)	0.0343 (17)	0.056 (2)	0.0037 (15)	0.0116 (18)	0.0101 (15)
C9	0.065 (2)	0.045 (2)	0.0461 (19)	−0.0019 (17)	0.0011 (18)	−0.0021 (16)
N1	0.0478 (16)	0.0323 (14)	0.0473 (16)	−0.0017 (11)	0.0060 (13)	0.0020 (12)
O1	0.103 (2)	0.0291 (13)	0.0731 (18)	0.0102 (13)	0.0036 (16)	−0.0032 (13)
O2	0.084 (2)	0.0502 (16)	0.0679 (18)	0.0132 (15)	−0.0051 (16)	0.0111 (14)
Br1	0.0514 (3)	0.0586 (3)	0.0511 (2)	0.00589 (17)	0.00106 (17)	−0.00134 (17)

Geometric parameters (Å, º) top

C1—C6	1.373 (5)	C5—Br1	1.900 (4)
C1—C2	1.398 (5)	C6—H6	0.9300
C1—C7	1.480 (5)	C7—O1	1.202 (4)
C2—C3	1.378 (5)	C7—C8	1.546 (6)
C2—N1	1.401 (5)	C8—O2	1.208 (5)
C3—C4	1.381 (5)	C8—N1	1.363 (4)
C3—H3	0.9300	C9—N1	1.461 (5)
C4—C5	1.389 (5)	C9—H9A	0.9600
C4—H4	0.9300	C9—H9B	0.9600
C5—C6	1.379 (5)	C9—H9C	0.9600

C6—C1—C2	121.8 (3)	C5—C6—H6	121.5
C6—C1—C7	132.0 (3)	O1—C7—C1	130.3 (4)
C2—C1—C7	106.1 (3)	O1—C7—C8	124.4 (3)
C3—C2—C1	120.9 (3)	C1—C7—C8	105.3 (3)
C3—C2—N1	127.6 (3)	O2—C8—N1	127.4 (4)
C1—C2—N1	111.5 (3)	O2—C8—C7	126.7 (3)
C2—C3—C4	117.3 (3)	N1—C8—C7	105.9 (3)
C2—C3—H3	121.3	N1—C9—H9A	109.5
C4—C3—H3	121.3	N1—C9—H9B	109.5
C3—C4—C5	121.4 (3)	H9A—C9—H9B	109.5
C3—C4—H4	119.3	N1—C9—H9C	109.5
C5—C4—H4	119.3	H9A—C9—H9C	109.5
C6—C5—C4	121.6 (3)	H9B—C9—H9C	109.5
C6—C5—Br1	120.4 (3)	C8—N1—C2	111.2 (3)
C4—C5—Br1	118.0 (3)	C8—N1—C9	124.9 (3)
C1—C6—C5	117.0 (3)	C2—N1—C9	123.8 (3)
C1—C6—H6	121.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2ⁱ	0.96	2.56	3.454 (5)	155
C9—H9C···O1ⁱⁱ	0.96	2.61	3.403 (5)	141

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2ⁱ	0.96	2.56	3.454 (5)	155.3
C9—H9C···O1ⁱⁱ	0.96	2.61	3.403 (5)	140.6

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

Experimental details

Crystal data
Chemical formula	C₉H₆BrNO₂
M_r	240.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.0634 (1), 11.9235 (3), 18.0978 (5)
β (°)	96.170 (2)
V (Å³)	871.76 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.68
Crystal size (mm)	0.57 × 0.22 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.452, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9696, 2022, 1606
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.102, 1.07
No. of reflections	2022
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.34

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

References

Aboul-Fadl, T., Bin-Jubair, F. A. S. & Aboul-Wafa, O. (2010). Eur. J. Med. Chem. 45, 4578–4586. Web of Science CAS PubMed Google Scholar
Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kharbach, Y., Kandri Rodi, Y., Renard, C., Essassi, E. M. & El Ammari, L. (2016). IUCrData, 1, x160559. Google Scholar
Pandeya, S. N., Sriram, D., Nath, G. & De Clercq, E. (1999). Eur. J. Med. Chem. 9, 25–31. CAS Google Scholar
Qachchachi, F.-Z., Kandri Rodi, Y., Essassi, E. M., Bodensteiner, M. & El Ammari, L. (2014). Acta Cryst. E70, o588. CSD CrossRef IUCr Journals Google Scholar
Qachchachi, F.-Z., Kandri Rodi, Y., Essassi, E. M., Kunz, W. & El Ammari, L. (2013). Acta Cryst. E69, o1801. CSD CrossRef IUCr Journals Google Scholar
Sarangapani, M. & Reddy, V. M. (1994). Indian J. Heterocycl. Chem. 3, 257–260. CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sridhar, S. K., Muniyandy, S. & Ramesh, A. (2001). Eur. J. Med. Chem. 36, 615–625. CrossRef PubMed CAS Google Scholar
Sridhar, S. K. & Sreenivasulu, M. (2001). Indian Drugs, 38, 531–534. CAS Google Scholar
Varma, M., Pandeya, S. N., Singh, K. N. & Stables, J. P. (2004). Acta Pharm. 54, 49–56. PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160792

doi:10.1107/S2414314616007926

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

5-Bromo-1-methyl­indoline-2,3-dione

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds

5-Bromo-1-methylindoline-2,3-dione