4-Bromo-3-hy­droxy-3-(4-hy­droxy-2-oxo-2H-chromen-3-yl)indolin-2-one

Zhu, S.-L.

doi:10.1107/S1600536811000213

4-Bromo-3-hydroxy-3-(4-hydroxy-2-oxo-2H-chromen-3-yl)indolin-2-one

In the molecule of the title compound, C₁₇H₁₀BrNO₅, the indoline system and the attached coumarin ring are each essentially planar with maximum deviations of 0.074 (2) and 0.062 (2) Å, respectively. The dihedral angle between them is 85.09 (3)°. In the crystal, all heteroatoms (except for the coumarin oxo O atoms) are involved in intra- and intermolecular hydrogen bonds. An intramolecular O—H

O hydrogen bond occurs. In the crystal, molecules are linked through O—H

O, N—H

O and C—H

O contacts, forming a complex three-dimensional structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811000213/bh2329sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811000213/bh2329Isup2.hkl Contains datablock I

CCDC reference: 631491

checkCIF report

Key indicators

Single-crystal X-ray study
T = 153 K
Mean (C-C) = 0.003 Å
R factor = 0.024
wR factor = 0.059
Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8     ..  O1      ..       2.61 Ang.

Alert level G
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.78 mm
PLAT793_ALERT_4_G The Model has Chirality at C1      (Verify) ....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The indole nucleus is a well known heterocycle (Da-Silva et al., 2001). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activities (Joshi & Chand, 1982). Coumarin and its derivatives are natural compounds and are also important chemicals in the perfume, cosmetic and pharmaceutical industries (Soine, 1964). As our interest in the synthesis of heterocyclic compounds, guided by the observation that the presence of two or more different heterocyclic moieties in a single molecule often remarkably enhances the biocidal profile, we investigated a simple and green protocol for the synthesis of indole and coumarin derivatives in water (Zhu, 2008). We report herein the crystal structure of the title compound.

In the molecule (Fig. 1), the indole ring (C1···C4/N1/C5···C8) and the attached coumarin ring (C9···C17/O3), are both planar. The dihedral angle between them is 85.09 (3)°. In the crystal structure, intermolecular and intramolecular O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background to indoles and their biological activity, see: Da-Silva et al. (2001); Joshi & Chand (1982). Coumarin and its derivatives are important in the perfume, cosmetic and pharmaceutical industries, see: Soine (1964). For the synthesis of indole and coumarin derivatives in water, see: Zhu (2008).

Experimental top

The title compound was prepared by the reaction of 4-bromoisatin (4-bromoindole-2,3-dione, 2 mmol) and 4-hydroxy-2H-chromen-2-one (2 mmol) in water (10 ml). The reaction was catalyzed by TEBAC (triethylbenzylammonium chloride, 1 mmol). After stirring at 333 K for 3 h, the reaction mixture was cooled and washed with small amount of ethanol. The crude product was filtered and single crystals of the title compound were obtained from an ethanol solution by slow evaporation at room temperature (yield: 80%; m.p. 469–471 K). Spectroscopic analysis: IR (KBr, ν, cm^-1): 3401, 3368, 3251, 3177, 2955, 1710, 1673, 1613, 1520, 1478, 1314, 1231, 1165, 1057, 922, 756, 612, 568. ¹H-NMR (400 MHz, DMSO-d₆): 9.88 (br s, 1H, NH), 7.84 (t, J = 7.2 Hz, 1H, ArH), 7.58-6.64 (m, 2H, ArH), 6.75-6.82 (m, 2H, ArH), 6.52- 6.59(m, 2H, ArH), 2.41(s, 1H, OH).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

4-Bromo-3-hydroxy-3-(4-hydroxy-2-oxo-2H-chromen-3-yl)indolin-2-one top

Crystal data top

C₁₇H₁₀BrNO₅	F(000) = 776
M_r = 388.17	D_x = 1.777 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 469–471 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71070 Å
a = 11.358 (3) Å	Cell parameters from 5845 reflections
b = 13.428 (3) Å	θ = 3.0–25.3°
c = 10.360 (2) Å	µ = 2.86 mm⁻¹
β = 113.307 (3)°	T = 153 K
V = 1451.1 (5) Å³	Block, colourless
Z = 4	0.78 × 0.36 × 0.35 mm

Data collection top

Rigaku Mercury diffractometer	2655 independent reflections
Radiation source: fine-focus sealed tube	2544 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.4°, θ_min = 3.0°
ω scans	h = −13→11
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −16→16
T_min = 0.173, T_max = 0.366	l = −12→12
13755 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0278P)² + 1.0659P] where P = (F_o² + 2F_c²)/3
2655 reflections	(Δ/σ)_max = 0.001
220 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³
0 constraints

Crystal data top

C₁₇H₁₀BrNO₅	V = 1451.1 (5) Å³
M_r = 388.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.358 (3) Å	µ = 2.86 mm⁻¹
b = 13.428 (3) Å	T = 153 K
c = 10.360 (2) Å	0.78 × 0.36 × 0.35 mm
β = 113.307 (3)°

Data collection top

Rigaku Mercury diffractometer	2655 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2544 reflections with I > 2σ(I)
T_min = 0.173, T_max = 0.366	R_int = 0.023
13755 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.08	Δρ_max = 0.34 e Å⁻³
2655 reflections	Δρ_min = −0.42 e Å⁻³
220 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.618858 (19)	0.424530 (16)	−0.05888 (2)	0.02468 (8)
O1	0.81967 (12)	0.24579 (9)	0.19817 (13)	0.0150 (3)
H1	0.8602	0.2544	0.1466	0.023*
O2	0.93364 (12)	0.28564 (10)	0.50987 (13)	0.0165 (3)
O3	0.55747 (12)	0.43528 (9)	0.37776 (13)	0.0147 (3)
O4	0.75296 (12)	0.48622 (9)	0.41805 (13)	0.0170 (3)
O5	0.58573 (13)	0.20063 (10)	0.13673 (14)	0.0195 (3)
H5	0.6572	0.1978	0.1306	0.029*
N1	1.01146 (14)	0.40717 (11)	0.40768 (16)	0.0144 (3)
H1A	1.0875	0.4158	0.4757	0.017*
C1	0.81079 (17)	0.33888 (13)	0.26299 (18)	0.0122 (4)
C2	0.92400 (17)	0.33989 (13)	0.41181 (19)	0.0130 (4)
C3	0.96558 (18)	0.46179 (14)	0.28075 (19)	0.0149 (4)
C4	0.84479 (18)	0.42644 (13)	0.19296 (19)	0.0131 (4)
C5	0.78170 (18)	0.47149 (14)	0.06449 (19)	0.0169 (4)
C6	0.8382 (2)	0.55024 (15)	0.0235 (2)	0.0223 (4)
H6	0.7943	0.5817	−0.0648	0.027*
C7	0.9589 (2)	0.58249 (15)	0.1123 (2)	0.0239 (5)
H7	0.9975	0.6359	0.0832	0.029*
C8	1.02526 (19)	0.53885 (15)	0.2429 (2)	0.0196 (4)
H8	1.1081	0.5613	0.3034	0.023*
C9	0.68273 (17)	0.34335 (13)	0.27623 (18)	0.0124 (4)
C10	0.66978 (17)	0.42446 (13)	0.35962 (19)	0.0124 (4)
C11	0.45996 (17)	0.36647 (14)	0.32443 (18)	0.0135 (4)
C12	0.46973 (17)	0.28643 (14)	0.24491 (18)	0.0139 (4)
C13	0.58467 (17)	0.27702 (14)	0.21777 (18)	0.0136 (4)
C14	0.37095 (18)	0.21509 (15)	0.20037 (19)	0.0176 (4)
H14	0.3758	0.1597	0.1457	0.021*
C15	0.26732 (18)	0.22596 (16)	0.2364 (2)	0.0203 (4)
H15	0.2014	0.1772	0.2084	0.024*
C16	0.25902 (18)	0.30829 (16)	0.3140 (2)	0.0214 (4)
H16	0.1864	0.3156	0.3370	0.026*
C17	0.35425 (18)	0.37954 (15)	0.35806 (19)	0.0178 (4)
H17	0.3476	0.4360	0.4100	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02298 (13)	0.02838 (13)	0.01533 (12)	−0.00237 (8)	−0.00025 (9)	0.00135 (8)
O1	0.0179 (7)	0.0140 (7)	0.0178 (7)	−0.0007 (5)	0.0120 (5)	−0.0031 (5)
O2	0.0181 (7)	0.0185 (7)	0.0146 (6)	0.0034 (5)	0.0084 (5)	0.0029 (5)
O3	0.0115 (6)	0.0166 (7)	0.0166 (7)	−0.0005 (5)	0.0061 (5)	−0.0045 (5)
O4	0.0156 (7)	0.0151 (7)	0.0192 (7)	−0.0024 (5)	0.0058 (5)	−0.0056 (5)
O5	0.0166 (7)	0.0213 (7)	0.0231 (7)	−0.0047 (6)	0.0106 (6)	−0.0118 (6)
N1	0.0099 (7)	0.0185 (8)	0.0131 (8)	−0.0012 (6)	0.0028 (6)	−0.0004 (6)
C1	0.0130 (9)	0.0116 (9)	0.0125 (9)	−0.0004 (7)	0.0057 (7)	−0.0017 (7)
C2	0.0125 (9)	0.0130 (9)	0.0157 (9)	0.0032 (7)	0.0078 (7)	−0.0013 (7)
C3	0.0159 (9)	0.0154 (9)	0.0153 (9)	0.0010 (7)	0.0082 (7)	−0.0021 (8)
C4	0.0153 (9)	0.0122 (9)	0.0143 (9)	−0.0005 (7)	0.0085 (8)	−0.0019 (7)
C5	0.0192 (10)	0.0174 (10)	0.0139 (9)	0.0005 (8)	0.0064 (8)	−0.0024 (8)
C6	0.0326 (12)	0.0192 (10)	0.0158 (10)	0.0000 (9)	0.0101 (9)	0.0038 (8)
C7	0.0338 (12)	0.0179 (10)	0.0256 (11)	−0.0060 (9)	0.0177 (10)	0.0002 (8)
C8	0.0204 (10)	0.0182 (10)	0.0226 (10)	−0.0061 (8)	0.0113 (8)	−0.0035 (8)
C9	0.0121 (9)	0.0136 (9)	0.0112 (9)	0.0009 (7)	0.0045 (7)	−0.0002 (7)
C10	0.0114 (9)	0.0141 (9)	0.0110 (9)	0.0008 (7)	0.0038 (7)	0.0018 (7)
C11	0.0111 (9)	0.0177 (9)	0.0089 (8)	−0.0008 (7)	0.0010 (7)	0.0011 (7)
C12	0.0128 (9)	0.0173 (9)	0.0102 (8)	0.0001 (7)	0.0031 (7)	0.0021 (7)
C13	0.0164 (9)	0.0137 (9)	0.0103 (8)	0.0012 (7)	0.0048 (7)	−0.0003 (7)
C14	0.0176 (9)	0.0185 (10)	0.0155 (9)	−0.0021 (8)	0.0051 (8)	−0.0023 (8)
C15	0.0129 (9)	0.0272 (11)	0.0191 (10)	−0.0068 (8)	0.0045 (8)	−0.0005 (8)
C16	0.0138 (9)	0.0339 (12)	0.0181 (10)	0.0004 (8)	0.0080 (8)	0.0008 (9)
C17	0.0153 (9)	0.0238 (10)	0.0143 (9)	0.0033 (8)	0.0056 (8)	−0.0016 (8)

Geometric parameters (Å, º) top

Br1—C5	1.8925 (19)	C6—C7	1.384 (3)
O1—C1	1.441 (2)	C6—H6	0.9500
O1—H1	0.8400	C7—C8	1.392 (3)
O2—C2	1.219 (2)	C7—H7	0.9500
O3—C10	1.369 (2)	C8—H8	0.9500
O3—C11	1.379 (2)	C9—C13	1.366 (3)
O4—C10	1.222 (2)	C9—C10	1.434 (2)
O5—C13	1.329 (2)	C11—C12	1.385 (3)
O5—H5	0.8400	C11—C17	1.387 (3)
N1—C2	1.356 (2)	C12—C14	1.407 (3)
N1—C3	1.413 (2)	C12—C13	1.446 (3)
N1—H1A	0.8800	C14—C15	1.376 (3)
C1—C4	1.510 (2)	C14—H14	0.9500
C1—C9	1.515 (2)	C15—C16	1.392 (3)
C1—C2	1.569 (2)	C15—H15	0.9500
C3—C8	1.376 (3)	C16—C17	1.379 (3)
C3—C4	1.395 (3)	C16—H16	0.9500
C4—C5	1.377 (3)	C17—H17	0.9500
C5—C6	1.388 (3)

C1—O1—H1	109.5	C3—C8—C7	117.08 (18)
C10—O3—C11	121.22 (14)	C3—C8—H8	121.5
C13—O5—H5	109.5	C7—C8—H8	121.5
C2—N1—C3	111.72 (15)	C13—C9—C10	120.16 (16)
C2—N1—H1A	124.1	C13—C9—C1	125.27 (16)
C3—N1—H1A	124.1	C10—C9—C1	114.56 (15)
O1—C1—C4	111.91 (14)	O4—C10—O3	116.09 (16)
O1—C1—C9	108.86 (14)	O4—C10—C9	124.78 (17)
C4—C1—C9	116.74 (15)	O3—C10—C9	119.13 (15)
O1—C1—C2	106.50 (14)	O3—C11—C12	121.17 (16)
C4—C1—C2	101.50 (14)	O3—C11—C17	116.90 (16)
C9—C1—C2	110.71 (14)	C12—C11—C17	121.91 (17)
O2—C2—N1	126.80 (17)	C11—C12—C14	118.83 (16)
O2—C2—C1	125.59 (16)	C11—C12—C13	118.33 (16)
N1—C2—C1	107.49 (15)	C14—C12—C13	122.75 (17)
C8—C3—C4	122.56 (18)	O5—C13—C9	125.02 (16)
C8—C3—N1	127.83 (17)	O5—C13—C12	115.15 (16)
C4—C3—N1	109.61 (16)	C9—C13—C12	119.82 (16)
C5—C4—C3	118.82 (17)	C15—C14—C12	119.70 (18)
C5—C4—C1	132.24 (17)	C15—C14—H14	120.2
C3—C4—C1	108.91 (16)	C12—C14—H14	120.2
C4—C5—C6	120.25 (18)	C14—C15—C16	120.10 (18)
C4—C5—Br1	120.15 (14)	C14—C15—H15	120.0
C6—C5—Br1	119.59 (15)	C16—C15—H15	120.0
C7—C6—C5	119.43 (19)	C17—C16—C15	121.25 (18)
C7—C6—H6	120.3	C17—C16—H16	119.4
C5—C6—H6	120.3	C15—C16—H16	119.4
C6—C7—C8	121.85 (19)	C16—C17—C11	118.19 (18)
C6—C7—H7	119.1	C16—C17—H17	120.9
C8—C7—H7	119.1	C11—C17—H17	120.9

C3—N1—C2—O2	−176.25 (17)	C2—C1—C9—C13	−125.59 (19)
C3—N1—C2—C1	7.53 (19)	O1—C1—C9—C10	170.24 (14)
O1—C1—C2—O2	−67.8 (2)	C4—C1—C9—C10	−61.9 (2)
C4—C1—C2—O2	175.02 (17)	C2—C1—C9—C10	53.5 (2)
C9—C1—C2—O2	50.4 (2)	C11—O3—C10—O4	−175.77 (15)
O1—C1—C2—N1	108.53 (15)	C11—O3—C10—C9	3.9 (2)
C4—C1—C2—N1	−8.69 (17)	C13—C9—C10—O4	178.59 (17)
C9—C1—C2—N1	−133.29 (15)	C1—C9—C10—O4	−0.5 (3)
C2—N1—C3—C8	176.71 (18)	C13—C9—C10—O3	−1.0 (3)
C2—N1—C3—C4	−3.0 (2)	C1—C9—C10—O3	179.82 (15)
C8—C3—C4—C5	−1.2 (3)	C10—O3—C11—C12	−3.1 (2)
N1—C3—C4—C5	178.55 (16)	C10—O3—C11—C17	174.87 (16)
C8—C3—C4—C1	177.16 (17)	O3—C11—C12—C14	176.13 (16)
N1—C3—C4—C1	−3.1 (2)	C17—C11—C12—C14	−1.7 (3)
O1—C1—C4—C5	71.8 (2)	O3—C11—C12—C13	−0.6 (3)
C9—C1—C4—C5	−54.5 (3)	C17—C11—C12—C13	−178.41 (17)
C2—C1—C4—C5	−174.98 (19)	C10—C9—C13—O5	178.61 (17)
O1—C1—C4—C3	−106.26 (17)	C1—C9—C13—O5	−2.4 (3)
C9—C1—C4—C3	127.40 (17)	C10—C9—C13—C12	−2.5 (3)
C2—C1—C4—C3	6.96 (18)	C1—C9—C13—C12	176.51 (16)
C3—C4—C5—C6	0.4 (3)	C11—C12—C13—O5	−177.70 (16)
C1—C4—C5—C6	−177.55 (18)	C14—C12—C13—O5	5.8 (3)
C3—C4—C5—Br1	179.05 (13)	C11—C12—C13—C9	3.3 (3)
C1—C4—C5—Br1	1.1 (3)	C14—C12—C13—C9	−173.22 (17)
C4—C5—C6—C7	0.6 (3)	C11—C12—C14—C15	−0.1 (3)
Br1—C5—C6—C7	−178.13 (15)	C13—C12—C14—C15	176.45 (17)
C5—C6—C7—C8	−0.7 (3)	C12—C14—C15—C16	1.4 (3)
C4—C3—C8—C7	1.0 (3)	C14—C15—C16—C17	−1.0 (3)
N1—C3—C8—C7	−178.66 (18)	C15—C16—C17—C11	−0.8 (3)
C6—C7—C8—C3	−0.1 (3)	O3—C11—C17—C16	−175.81 (16)
O1—C1—C9—C13	−8.8 (2)	C12—C11—C17—C16	2.1 (3)
C4—C1—C9—C13	119.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.98	2.7672 (17)	155
O5—H5···O1	0.84	1.81	2.5486 (19)	145
N1—H1A···O4ⁱⁱ	0.88	2.16	2.940 (2)	148
C7—H7···O2ⁱⁱⁱ	0.95	2.49	3.429 (2)	172
C8—H8···O1ⁱⁱⁱ	0.95	2.61	3.217 (2)	122

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₀BrNO₅
M_r	388.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	11.358 (3), 13.428 (3), 10.360 (2)
β (°)	113.307 (3)
V (Å³)	1451.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.86
Crystal size (mm)	0.78 × 0.36 × 0.35

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.173, 0.366
No. of measured, independent and observed [I > 2σ(I)] reflections	13755, 2655, 2544
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.059, 1.08
No. of reflections	2655
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.42

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).