5-Bromo-1-(4-bromo­phen­yl)isatin

El-Hiti, G.A.; Smith, K.; Alamri, M.; Morris, C.A.; Kille, P.; Kariuki, B.M.

doi:10.1107/S2414314618004261

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180426

https://doi.org/10.1107/S2414314618004261

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5-Bromo-1-(4-bromophenyl)isatin

Gamal A. El-Hiti,^a ^* Keith Smith,^b Mesfer Alamri,^c Ceri A. Morris,^d Peter Kille ^c and Benson M. Kariuki ^b

^aCornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, ^bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK, ^cSchool of Biosciences, Cardiff University, Cardiff CF10 3AT, UK, and ^dSchool of Medicine, Cardiff University, Tenovus Building, Heath Park, Cardiff CF14 4XN, UK
^*Correspondence e-mail: gelhiti@ksu.edu.sa

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 8 March 2018; accepted 13 March 2018; online 15 March 2018)

In the title compound [systematic name: 5-bromo-1-(4-bromophenyl)-2,3-dihydro-1H-indole-2,3-dione], C₁₄H₇Br₂NO₂, all of the atoms except the C—H groups in the bromobenzene ring lie on a (010) crystallographic mirror plane, with the benzene ring completed by reflection. The dihedral angle between the ring systems is constrained to be 90° by symmetry. In the crystal, molecules are linked by weak C—H⋯Br interactions in the [001] direction and paired very weak C—H⋯O interactions to the same acceptor in the [100] direction, generating (010) sheets. Possible extremely weak π–π stacking occurs between the layers.

Keywords: crystal structure; isatin; hydrogen bonding.

CCDC reference: 1829295

Structure description

A number of synthetic procedures have been established for obtaining isatins. These include reactions of N′-(2-bromoaryl)-N,N-dimethylureas with methyllithium (1.1 molar equivalents) and tert-butyllithium (2.2 molar equivalents) at 0°C followed by treatment with carbon monoxide (Smith et al., 1999 , 2003 ), oxidative cyclization of 2′-aminoacetophenones by use of iodine and tert-butyl hydroperoxide (TBHP) (Ilangovan & Satish, 2014 ) or aqueous copper(II) acetate in dimethyl sulfoxide (DMSO) at 80°C for 4–10 h (Ilangovan & Satish, 2013 ), oxidative amidation of 2′-aminophenylacetylenes in the presence of I₂ in DMSO at 100°C for 5–12 h (Satish et al., 2015 ), oxidation of indoles with I₂/TBHP in DMSO at 80°C for 24 h (Zi et al., 2014 ), or reactions of diarylamines with oxalyl chloride (Bryant et al., 1993 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound.

All the atoms except C10 and C11 lie on a (010) crystallographic mirror plane, with the benzene ring completed by reflection (Fig. 1). The dihedral angle between the ring systems is constrained to be 90° by symmetry. In the crystal, the molecules are linked by weak C—H⋯Br interactions (Table 1) in the [001] direction and paired C—H⋯O interactions to the same acceptor in the [100] direction, generating (010) sheets (Fig. 2). The layers are stacked along the b axis, resulting in possible extremely weak π–π overlap between neighbouring bromoisatino groups (Fig. 3). The centroid-to-centroid distance between adjacent isatin units is 4.431 (2) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.93	2.68	3.296 (6)	124
C3—H3⋯O2ⁱ	0.93	2.70	3.312 (7)	124
C5—H5⋯Br2ⁱⁱ	0.93	2.84	3.763 (5)	173
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) x, y, z+1.

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids.

Figure 2
Intermolecular interactions (dashed lines) in a layer of the structure.

Figure 3
Crystal packing viewed along the b axis.

Synthesis and crystallization

A solution of bis(4-bromophenyl)amine in dichloromethane (DCM) was added dropwise to a stirred, boiling solution of oxalyl chloride (2.0 mole equivalents) in DCM. The mixture was heated under reflux for 1 h and the volatiles were removed under reduced pressure. To the residue obtained, DCM and excess anhydrous aluminium chloride (2.2 molar equivalents in portions) were added and the mixture was refluxed for 1 h. Dichloromethane was removed under reduced pressure and dilute hydrochloric acid (1 M) was added and the mixture was stirred for 30 min. The product was extracted with DCM, dried over anhydrous magnesium sulfate and the solvent was removed under vacuum to give the essentially pure product in 91% yield. Recrystallization from acetonitrile solution gave the title compound as orange crystals (m.p. 235–236°C).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₇Br₂NO₂
M_r	381.03
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	15.1160 (14), 6.8728 (6), 12.7492 (11)
V (Å³)	1324.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	6.12
Crystal size (mm)	0.29 × 0.24 × 0.19

Data collection
Diffractometer	Agilent SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.377, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5624, 1801, 1174
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.096, 1.06
No. of reflections	1801
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.59
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Oxford Diffraction, Yarnton, England.]$ ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ).

Structural data

CCDC reference: 1829295

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004261/hb4216sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004261/hb4216Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618004261/hb4216Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

5-Bromo-1-(4-bromophenyl)-2,3-dihydro-1H-indole-2,3-dione top

Crystal data top

C₁₄H₇Br₂NO₂	D_x = 1.911 Mg m⁻³
M_r = 381.03	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1378 reflections
a = 15.1160 (14) Å	θ = 4.3–25.8°
b = 6.8728 (6) Å	µ = 6.12 mm⁻¹
c = 12.7492 (11) Å	T = 293 K
V = 1324.5 (2) Å³	Block, orange
Z = 4	0.29 × 0.24 × 0.19 mm
F(000) = 736

Data collection top

Agilent SuperNova, Dual, Cu at zero, Atlas diffractometer	1174 reflections with I > 2σ(I)
ω scans	R_int = 0.041
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	θ_max = 30.0°, θ_min = 3.4°
T_min = 0.377, T_max = 1.000	h = −14→20
5624 measured reflections	k = −6→9
1801 independent reflections	l = −16→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0277P)² + 1.353P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.53 e Å⁻³
1801 reflections	Δρ_min = −0.59 e Å⁻³
110 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0052 (4)
Primary atom site location: structure-invariant direct methods

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.

Refinement. All H atoms were placed in calculated positions and refined using a riding model. C—H bonds were fixed at 0.93 Å and U_iso(H) set to 1.2Ueq(C).

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

	x	y	z	U_iso*/U_eq
C1	0.5530 (3)	0.250000	0.3519 (4)	0.0438 (12)
C2	0.4652 (3)	0.250000	0.3236 (4)	0.0476 (12)
H2	0.448493	0.250000	0.253441	0.057*
C3	0.4023 (4)	0.250000	0.4030 (4)	0.0501 (13)
H3	0.342467	0.250000	0.385924	0.060*
C4	0.4276 (3)	0.250000	0.5072 (4)	0.0429 (11)
C5	0.5158 (3)	0.250000	0.5361 (4)	0.0433 (12)
H5	0.532555	0.250000	0.606269	0.052*
C6	0.5780 (3)	0.250000	0.4567 (4)	0.0421 (11)
C7	0.6743 (3)	0.250000	0.4607 (4)	0.0480 (12)
C8	0.7050 (4)	0.250000	0.3443 (5)	0.0516 (13)
C9	0.6233 (3)	0.250000	0.1732 (4)	0.0469 (12)
C10	0.6218 (4)	0.0790 (6)	0.1197 (3)	0.0771 (14)
H10	0.625054	−0.038212	0.155897	0.092*
C11	0.6156 (4)	0.0789 (7)	0.0112 (4)	0.0831 (15)
H11	0.613968	−0.037843	−0.025692	0.100*
C12	0.6118 (3)	0.250000	−0.0401 (4)	0.0535 (14)
N1	0.6283 (3)	0.250000	0.2857 (3)	0.0484 (10)
O1	0.7242 (2)	0.250000	0.5347 (3)	0.0650 (11)
O2	0.7799 (3)	0.250000	0.3124 (3)	0.0666 (11)
Br1	0.33910 (4)	0.250000	0.61293 (5)	0.0564 (2)
Br2	0.60700 (6)	0.250000	−0.18928 (5)	0.0946 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.055 (3)	0.038 (2)	0.039 (3)	0.000	−0.003 (2)	0.000
C2	0.053 (3)	0.055 (3)	0.035 (3)	0.000	−0.005 (2)	0.000
C3	0.050 (3)	0.053 (3)	0.048 (3)	0.000	−0.005 (2)	0.000
C4	0.049 (3)	0.041 (3)	0.039 (3)	0.000	0.003 (2)	0.000
C5	0.058 (3)	0.040 (3)	0.032 (3)	0.000	−0.009 (2)	0.000
C6	0.051 (3)	0.038 (2)	0.037 (3)	0.000	−0.005 (2)	0.000
C7	0.052 (3)	0.047 (3)	0.045 (3)	0.000	−0.011 (2)	0.000
C8	0.055 (4)	0.048 (3)	0.052 (3)	0.000	−0.002 (3)	0.000
C9	0.050 (3)	0.052 (3)	0.039 (3)	0.000	0.001 (2)	0.000
C10	0.135 (4)	0.050 (2)	0.046 (3)	0.007 (3)	−0.007 (3)	0.002 (2)
C11	0.136 (5)	0.063 (3)	0.050 (3)	0.010 (3)	−0.013 (3)	−0.010 (2)
C12	0.049 (3)	0.074 (4)	0.037 (3)	0.000	−0.006 (2)	0.000
N1	0.054 (3)	0.053 (2)	0.038 (3)	0.000	0.001 (2)	0.000
O1	0.059 (2)	0.081 (3)	0.055 (3)	0.000	−0.013 (2)	0.000
O2	0.049 (2)	0.085 (3)	0.066 (3)	0.000	0.0106 (19)	0.000
Br1	0.0597 (4)	0.0578 (3)	0.0518 (4)	0.000	0.0100 (3)	0.000
Br2	0.1138 (7)	0.1280 (7)	0.0420 (4)	0.000	−0.0233 (4)	0.000

Geometric parameters (Å, º) top

C1—C2	1.374 (7)	C7—O1	1.208 (6)
C1—C6	1.389 (7)	C7—C8	1.554 (8)
C1—N1	1.418 (6)	C8—O2	1.203 (6)
C2—C3	1.390 (7)	C8—N1	1.379 (7)
C2—H2	0.9300	C9—C10ⁱ	1.359 (5)
C3—C4	1.382 (7)	C9—C10	1.359 (5)
C3—H3	0.9300	C9—N1	1.436 (6)
C4—C5	1.383 (7)	C10—C11	1.386 (6)
C4—Br1	1.899 (5)	C10—H10	0.9300
C5—C6	1.381 (7)	C11—C12	1.347 (5)
C5—H5	0.9300	C11—H11	0.9300
C6—C7	1.457 (7)	C12—Br2	1.904 (6)

C2—C1—C6	121.0 (5)	C6—C7—C8	105.4 (4)
C2—C1—N1	128.3 (5)	O2—C8—N1	127.4 (6)
C6—C1—N1	110.7 (4)	O2—C8—C7	127.1 (5)
C1—C2—C3	118.0 (5)	N1—C8—C7	105.5 (4)
C1—C2—H2	121.0	C10ⁱ—C9—C10	119.7 (5)
C3—C2—H2	121.0	C10ⁱ—C9—N1	120.2 (3)
C4—C3—C2	120.7 (5)	C10—C9—N1	120.2 (3)
C4—C3—H3	119.7	C9—C10—C11	120.2 (4)
C2—C3—H3	119.7	C9—C10—H10	119.9
C3—C4—C5	121.5 (5)	C11—C10—H10	119.9
C3—C4—Br1	119.2 (4)	C12—C11—C10	119.1 (4)
C5—C4—Br1	119.3 (4)	C12—C11—H11	120.5
C6—C5—C4	117.5 (4)	C10—C11—H11	120.5
C6—C5—H5	121.3	C11ⁱ—C12—C11	121.7 (6)
C4—C5—H5	121.3	C11ⁱ—C12—Br2	119.1 (3)
C5—C6—C1	121.3 (5)	C11—C12—Br2	119.1 (3)
C5—C6—C7	130.9 (5)	C8—N1—C1	110.6 (4)
C1—C6—C7	107.8 (5)	C8—N1—C9	125.9 (4)
O1—C7—C6	130.6 (5)	C1—N1—C9	123.5 (4)
O1—C7—C8	124.0 (5)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱⁱ	0.93	2.68	3.296 (6)	124
C3—H3···O2ⁱⁱ	0.93	2.70	3.312 (7)	124
C5—H5···Br2ⁱⁱⁱ	0.93	2.84	3.763 (5)	173

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

Funding information

We thank the EPSRC for the grant that supplied the MS instrumentation used in this study. MA thanks the Saudi Arabian Cultural Bureau, London for a scholarship and GAEH thanks King Saud University, Deanship of Scientific Research, Research Chairs for funding his research.

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