5-Bromo-1-(6-bromo­hex­yl)indoline-2,3-dione

Kharbach, Y.; Kandri Rodi, Y.; Haoudi, A.; Essassi, E.M.; Capet, F.; Zouihri, H.

doi:10.1107/S241431461600883X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160883

doi:10.1107/S241431461600883X

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5-Bromo-1-(6-bromohexyl)indoline-2,3-dione

Yassine Kharbach,^a Youssef Kandri Rodi,^a Amal Haoudi,^a ^* El Mokhtar Essassi,^b Frédéric Capet ^c and Hafid Zouihri ^d

^aLaboratoire de Chimie Organique, Faculté des Sciences Dhar el Mahraz, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, ^bLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014, Avenue Ibn Batouta, Rabat, Morocco, ^cUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, France, and ^dDépartement de Chimie, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, 80000 Agadir, Morocco
^*Correspondence e-mail: haoudi_amal@yahoo.fr

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 31 May 2016; accepted 31 May 2016; online 17 June 2016)

In the title compound, C₁₄H₁₅Br₂NO₂, the dihedral angle between the mean plane passing through the bromohexyl chain and the 5-bromoindoline ring system (r.m.s. deviation = 0.044Å) is 70.0 (3)°. In the crystal, molecules are connected by C—H⋯O hydrogen bonds, generating zigzag chains propagating along [010]. The packing is also influenced by inter-chain π–π interactions which form layers parallel to the ab plane [centroid–centroid distances = 3.765 (2) Å].

Keywords: crystal structure; indoline-2,3-dione; chains; hydrogen bonds.

CCDC reference: 1482861

Structure description

Isatin derivatives have a wide range of biological properties and show pharmacological activity against bacteria and fungi (Pandeya et al., 2005 ; Vine et al., 2007 ). The most demanding prospect of research surrounding isatin derivatives has evolved in the context of their antifungal and antiviral activities (Aboul-Fadl et al., 2010 ). The significance of isatin derivatives has even been extended to the design of novel anticancer drugs (Rodríuez-Argüelles et al., 2004 ), and recently, a number of isatin-based compounds have been reported to be inhibitors of caspase-3 and caspase-7 (Chu et al., 2007 ). As part of a continuing study on halogenated isatins (Kharbach et al., 2016a , Kharbach et al., 2016b ), the structures of N-substituted derivatives of isatin have been reported using 1,3-dibromopropane (Qachchachi et al., 2016 ). Herein, we report the crystal structure of 5-bromo-1-(6-bromohexyl)indoline-2,3-dione, obtained using 1,6-dibromohexane as an alkylating agent as part of our work to develop new 5-bromoisatin derivatives.

In the title compound (Fig. 1), the dihedral angle between the mean plane passing through the bromohexyl chain and the 5-bromo-indoline ring system (r.m.s. deviation: 0.044 Å is 70.0 (3)°. In the crystal, molecules are connected by C—H⋯O hydrogen bonds (Table 1), generating zigzag chains propagating in the [010] direction. The packing (Fig. 2) is also influenced by inter-chain π–π interactions which form layers parallel to the ab plane [centroid-centroid distances = 3.765 (2) Å].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.93	2.58	3.406 (5)	148
C10—H10A⋯O1ⁱⁱ	0.97	2.53	3.364 (5)	143
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The crystal structure of the title compound, viewed along the c axis, showing zigzag chains parallel to the b axis linked by C— H⋯O hydrogen bonds (dashed lines).

Synthesis and crystallization

To a solution of 5-bromoisatin (0.4 g, 1.76 mmol) and 1,6-dibromohexane (0,31 ml, 1.95 mmol) in DMF (25 ml), was added tetra-n-butylammonium bromide (0.1 g, 0.4 mmol) and potassium carbonate (0.6 g, 4.4 mmol). The reaction mixture was stirred for 48 h. After filtering, the solution was evaporated in reduced pressure. The title compound was obtained in 84% yield and recrystallized from ethanol solution to afford orange crystals (m.p. 355 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₅Br₂NO₂
M_r	389.09
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	299
a, b, c (Å)	4.6344 (2), 12.6284 (6), 25.3537 (12)
V (Å³)	1483.83 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.46
Crystal size (mm)	0.22 × 0.11 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.576, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	28990, 3663, 2699
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.072, 1.02
No. of reflections	3663
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.52
Absolute structure	Flack x determined using 932 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.006 (4)
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXT (Sheldrick, 2015 ), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1482861

Crystal structure: contains datablock I. DOI: 10.1107/S241431461600883X/bt4013sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461600883X/bt4013Isup2.hkl

Supporting information file. DOI: 10.1107/S241431461600883X/bt4013Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

5-Bromo-1-(6-bromohexyl)indoline-2,3-dione top

Crystal data top

C₁₄H₁₅Br₂NO₂	D_x = 1.742 Mg m⁻³
M_r = 389.09	Melting point: 355 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8821 reflections
a = 4.6344 (2) Å	θ = 2.9–23.7°
b = 12.6284 (6) Å	µ = 5.46 mm⁻¹
c = 25.3537 (12) Å	T = 299 K
V = 1483.83 (12) Å³	Platelet, orange
Z = 4	0.22 × 0.11 × 0.05 mm
F(000) = 768

Data collection top

Bruker APEXII CCD diffractometer	2699 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.039
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 28.3°, θ_min = 1.6°
T_min = 0.576, T_max = 0.746	h = −6→6
28990 measured reflections	k = −16→15
3663 independent reflections	l = −33→33

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0272P)² + 0.7737P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3663 reflections	Δρ_max = 0.45 e Å⁻³
172 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 932 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.006 (4)

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
Br1	0.97543 (11)	0.74683 (4)	0.93893 (2)	0.06086 (16)
Br2	0.48372 (15)	0.60074 (4)	0.45917 (2)	0.07524 (19)
C1	0.7295 (9)	0.7167 (3)	0.88077 (16)	0.0400 (10)
C2	0.6607 (10)	0.7974 (3)	0.84574 (17)	0.0420 (10)
H2	0.7425	0.8641	0.8502	0.050*
C3	0.4716 (11)	0.7800 (3)	0.80417 (15)	0.0403 (9)
H3	0.4225	0.8342	0.7810	0.048*
C4	0.3591 (8)	0.6796 (3)	0.79838 (14)	0.0317 (9)
C5	0.4348 (8)	0.5988 (3)	0.83316 (14)	0.0342 (9)
C6	0.6199 (9)	0.6160 (3)	0.87463 (16)	0.0399 (10)
H6	0.6693	0.5616	0.8977	0.048*
C7	0.2780 (10)	0.5037 (3)	0.81645 (16)	0.0391 (9)
C8	0.0976 (10)	0.5385 (3)	0.76811 (17)	0.0429 (11)
C9	0.0365 (10)	0.7071 (3)	0.71786 (15)	0.0414 (9)
H9A	−0.0100	0.7767	0.7317	0.050*
H9B	−0.1422	0.6743	0.7065	0.050*
C10	0.2323 (9)	0.7199 (3)	0.67068 (16)	0.0407 (10)
H10A	0.4080	0.7550	0.6819	0.049*
H10B	0.1379	0.7654	0.6452	0.049*
C11	0.3121 (10)	0.6165 (3)	0.64382 (16)	0.0416 (10)
H11A	0.1374	0.5769	0.6364	0.050*
H11B	0.4292	0.5745	0.6677	0.050*
C12	0.4772 (11)	0.6332 (3)	0.59266 (16)	0.0496 (10)
H12A	0.3580	0.6738	0.5686	0.060*
H12B	0.6490	0.6745	0.6000	0.060*
C13	0.5652 (11)	0.5312 (4)	0.56595 (17)	0.0553 (12)
H13A	0.6842	0.4908	0.5902	0.066*
H13B	0.3929	0.4899	0.5590	0.066*
C14	0.7274 (12)	0.5448 (5)	0.5153 (2)	0.0712 (15)
H14A	0.8053	0.4769	0.5044	0.085*
H14B	0.8881	0.5927	0.5210	0.085*
N1	0.1629 (7)	0.6432 (2)	0.76016 (13)	0.0353 (7)
O1	0.2758 (8)	0.4155 (2)	0.83436 (13)	0.0592 (9)
O2	−0.0693 (8)	0.4850 (2)	0.74288 (13)	0.0603 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0551 (3)	0.0779 (3)	0.0496 (3)	−0.0053 (3)	−0.0101 (3)	−0.0151 (2)
Br2	0.0904 (4)	0.0907 (4)	0.0447 (3)	0.0124 (4)	0.0123 (3)	0.0084 (2)
C1	0.035 (2)	0.047 (2)	0.038 (2)	0.0017 (18)	−0.0012 (19)	−0.0089 (19)
C2	0.047 (2)	0.035 (2)	0.045 (3)	−0.0051 (19)	0.006 (2)	−0.0083 (19)
C3	0.050 (2)	0.0298 (18)	0.041 (2)	0.001 (2)	0.000 (2)	0.0024 (14)
C4	0.035 (2)	0.0316 (19)	0.028 (2)	0.0048 (16)	0.0040 (17)	−0.0029 (15)
C5	0.039 (2)	0.0302 (17)	0.0330 (19)	0.0030 (17)	0.0041 (17)	−0.0016 (15)
C6	0.047 (2)	0.037 (2)	0.035 (2)	0.0071 (18)	0.0012 (18)	0.0037 (18)
C7	0.047 (2)	0.034 (2)	0.036 (2)	−0.0003 (18)	0.005 (2)	0.0000 (17)
C8	0.051 (3)	0.036 (2)	0.042 (2)	−0.002 (2)	0.006 (2)	−0.0039 (19)
C9	0.042 (2)	0.0414 (19)	0.041 (2)	0.007 (2)	−0.004 (2)	−0.0021 (16)
C10	0.047 (2)	0.036 (2)	0.040 (2)	0.0064 (17)	−0.002 (2)	0.0052 (17)
C11	0.045 (2)	0.044 (2)	0.036 (2)	0.005 (2)	−0.0016 (19)	0.0003 (18)
C12	0.054 (3)	0.052 (2)	0.043 (2)	0.000 (3)	0.001 (3)	0.0028 (17)
C13	0.064 (3)	0.061 (3)	0.040 (2)	0.013 (2)	0.004 (2)	0.000 (2)
C14	0.063 (3)	0.094 (4)	0.056 (3)	0.015 (3)	0.008 (3)	−0.009 (3)
N1	0.0437 (19)	0.0297 (16)	0.0325 (18)	−0.0013 (14)	−0.0024 (15)	0.0004 (14)
O1	0.083 (3)	0.0332 (16)	0.062 (2)	−0.0068 (16)	−0.0018 (19)	0.0053 (14)
O2	0.071 (3)	0.0488 (18)	0.061 (2)	−0.0179 (18)	−0.0154 (19)	−0.0060 (15)

Geometric parameters (Å, º) top

Br1—C1	1.902 (4)	C9—C10	1.510 (6)
Br2—C14	1.949 (5)	C9—H9A	0.9700
C1—C6	1.379 (6)	C9—H9B	0.9700
C1—C2	1.389 (6)	C10—C11	1.518 (5)
C2—C3	1.388 (6)	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700
C3—C4	1.379 (5)	C11—C12	1.521 (6)
C3—H3	0.9300	C11—H11A	0.9700
C4—C5	1.393 (5)	C11—H11B	0.9700
C4—N1	1.406 (5)	C12—C13	1.511 (6)
C5—C6	1.374 (6)	C12—H12A	0.9700
C5—C7	1.466 (6)	C12—H12B	0.9700
C6—H6	0.9300	C13—C14	1.498 (7)
C7—O1	1.203 (5)	C13—H13A	0.9700
C7—C8	1.547 (6)	C13—H13B	0.9700
C8—O2	1.210 (5)	C14—H14A	0.9700
C8—N1	1.371 (5)	C14—H14B	0.9700
C9—N1	1.465 (5)

C6—C1—C2	121.3 (4)	C11—C10—H10A	108.7
C6—C1—Br1	119.5 (3)	C9—C10—H10B	108.7
C2—C1—Br1	119.1 (3)	C11—C10—H10B	108.7
C3—C2—C1	120.9 (4)	H10A—C10—H10B	107.6
C3—C2—H2	119.5	C10—C11—C12	112.7 (3)
C1—C2—H2	119.5	C10—C11—H11A	109.1
C4—C3—C2	117.7 (3)	C12—C11—H11A	109.1
C4—C3—H3	121.1	C10—C11—H11B	109.1
C2—C3—H3	121.1	C12—C11—H11B	109.1
C3—C4—C5	120.7 (4)	H11A—C11—H11B	107.8
C3—C4—N1	128.2 (3)	C13—C12—C11	113.6 (3)
C5—C4—N1	111.1 (3)	C13—C12—H12A	108.9
C6—C5—C4	121.8 (3)	C11—C12—H12A	108.9
C6—C5—C7	131.2 (4)	C13—C12—H12B	108.9
C4—C5—C7	107.0 (3)	C11—C12—H12B	108.9
C5—C6—C1	117.5 (4)	H12A—C12—H12B	107.7
C5—C6—H6	121.3	C14—C13—C12	114.9 (4)
C1—C6—H6	121.3	C14—C13—H13A	108.5
O1—C7—C5	130.8 (4)	C12—C13—H13A	108.5
O1—C7—C8	123.9 (4)	C14—C13—H13B	108.5
C5—C7—C8	105.3 (3)	C12—C13—H13B	108.5
O2—C8—N1	127.0 (4)	H13A—C13—H13B	107.5
O2—C8—C7	127.3 (4)	C13—C14—Br2	112.2 (3)
N1—C8—C7	105.7 (3)	C13—C14—H14A	109.2
N1—C9—C10	113.5 (4)	Br2—C14—H14A	109.2
N1—C9—H9A	108.9	C13—C14—H14B	109.2
C10—C9—H9A	108.9	Br2—C14—H14B	109.2
N1—C9—H9B	108.9	H14A—C14—H14B	107.9
C10—C9—H9B	108.9	C8—N1—C4	110.9 (3)
H9A—C9—H9B	107.7	C8—N1—C9	123.4 (3)
C9—C10—C11	114.2 (3)	C4—N1—C9	125.6 (3)
C9—C10—H10A	108.7

C6—C1—C2—C3	2.0 (7)	C5—C7—C8—O2	−178.0 (4)
Br1—C1—C2—C3	−177.0 (3)	O1—C7—C8—N1	−179.4 (4)
C1—C2—C3—C4	−1.2 (6)	C5—C7—C8—N1	1.2 (4)
C2—C3—C4—C5	−0.2 (6)	N1—C9—C10—C11	60.9 (5)
C2—C3—C4—N1	179.2 (4)	C9—C10—C11—C12	172.7 (4)
C3—C4—C5—C6	0.8 (6)	C10—C11—C12—C13	178.6 (4)
N1—C4—C5—C6	−178.7 (4)	C11—C12—C13—C14	179.8 (4)
C3—C4—C5—C7	179.6 (4)	C12—C13—C14—Br2	−69.3 (5)
N1—C4—C5—C7	0.1 (4)	O2—C8—N1—C4	178.0 (4)
C4—C5—C6—C1	0.0 (6)	C7—C8—N1—C4	−1.2 (4)
C7—C5—C6—C1	−178.4 (4)	O2—C8—N1—C9	−0.7 (7)
C2—C1—C6—C5	−1.4 (6)	C7—C8—N1—C9	−179.9 (4)
Br1—C1—C6—C5	177.7 (3)	C3—C4—N1—C8	−178.7 (4)
C6—C5—C7—O1	−1.6 (8)	C5—C4—N1—C8	0.8 (5)
C4—C5—C7—O1	179.9 (5)	C3—C4—N1—C9	−0.1 (6)
C6—C5—C7—C8	177.9 (4)	C5—C4—N1—C9	179.4 (4)
C4—C5—C7—C8	−0.7 (4)	C10—C9—N1—C8	−100.0 (5)
O1—C7—C8—O2	1.5 (7)	C10—C9—N1—C4	81.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.93	2.58	3.406 (5)	148
C10—H10A···O1ⁱⁱ	0.97	2.53	3.364 (5)	143

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

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