Methyl 4-(4-bromo-anilino)-2',5-dioxo-5H-spiro-[furan-2,3'-indoline]-3-carboxyl-ate.

In the title compound, C19H13BrN2O5, the spiro furan ring is almost planar with a maximum deviation of 0.034 (2) Å. The indole unit and the furan ring are normal to each other, making a dihedral angle of 87.82 (8) °. The mol-ecular structure is stabilized by an intra-molecular N-H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, mol-ecules are linked via pairs of N-H⋯O hydrogen bonds, forming inversion dimers enclosing R (2) 2(8) ring motifs.

Related literature

For applications of oxindoles, see: Akai et al. (2004 ▶); Gallagher et al. (1985 ▶); Tokunaga et al. (2001 ▶); Zaveri et al. (2004 ▶). For applications of tetra­hydro­furans, see: Garzino et al. (2000 ▶). For a related structure, see: Gangadharan et al. (2013 ▶). For the length of a C—Br single bond, see: Koşar et al. (2006 ▶). For resonance structure in a carboxyl­ate group, see: Merlino (1971 ▶); Varghese et al. (1986 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C19H13BrN2O5

M = 429.21

Triclinic,

a = 7.845 (5) Å

b = 8.365 (5) Å

c = 13.703 (5) Å

α = 81.565 (5)°

β = 81.944 (5)°

γ = 76.183 (5)°

V = 858.6 (8) Å3

Z = 2

Mo Kα radiation

μ = 2.43 mm−1

T = 296 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.487, T max = 0.615

19580 measured reflections

5243 independent reflections

3611 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.095

S = 1.02

5243 reflections

251 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814001329/su2688sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001329/su2688Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814001329/su2688Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H13BrN2O5	Z = 2
Mr = 429.21	F(000) = 432
Triclinic, P1	Dx = 1.660 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.845 (5) Å	Cell parameters from 3611 reflections
b = 8.365 (5) Å	θ = 2.5–30.7°
c = 13.703 (5) Å	µ = 2.43 mm−1
α = 81.565 (5)°	T = 296 K
β = 81.944 (5)°	Block, yellow
γ = 76.183 (5)°	0.30 × 0.25 × 0.20 mm
V = 858.6 (8) Å3

Bruker SMART APEXII area-detector diffractometer	5243 independent reflections
Radiation source: fine-focus sealed tube	3611 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω and φ scans	θmax = 30.7°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.487, Tmax = 0.615	k = −10→11
19580 measured reflections	l = −19→19

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0509P)2 + 0.0269P] where P = (Fo2 + 2Fc2)/3
5243 reflections	(Δ/σ)max = 0.001
251 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	−0.4990 (3)	0.6472 (2)	0.90768 (17)	0.0504 (5)
H1	−0.5215	0.6959	0.9664	0.060*
C2	−0.6306 (3)	0.6597 (3)	0.8475 (2)	0.0582 (6)
H2	−0.7443	0.7179	0.8665	0.070*
C3	−0.5985 (3)	0.5890 (2)	0.76091 (18)	0.0558 (6)
H3	−0.6902	0.5995	0.7225	0.067*
C4	−0.4295 (3)	0.5013 (2)	0.72958 (16)	0.0466 (5)
H4	−0.4066	0.4538	0.6705	0.056*
C5	−0.2984 (2)	0.48741 (19)	0.78896 (13)	0.0364 (4)
C6	−0.3335 (2)	0.5594 (2)	0.87638 (13)	0.0380 (4)
C7	−0.0421 (2)	0.4317 (2)	0.87382 (12)	0.0337 (4)
C8	−0.1067 (2)	0.40203 (19)	0.77657 (12)	0.0332 (3)
C9	0.0787 (2)	0.3804 (2)	0.62970 (13)	0.0370 (4)
C10	0.0397 (2)	0.2139 (2)	0.66609 (12)	0.0340 (4)
C11	−0.0593 (2)	0.22549 (19)	0.75528 (12)	0.0329 (3)
C12	−0.0965 (2)	0.0843 (2)	0.82184 (12)	0.0334 (3)
C13	−0.2248 (3)	−0.0121 (2)	0.97751 (15)	0.0555 (5)
H13A	−0.3023	−0.0637	0.9511	0.083*
H13B	−0.2802	0.0271	1.0392	0.083*
H13C	−0.1165	−0.0913	0.9885	0.083*
C14	0.2003 (2)	0.0426 (2)	0.53099 (13)	0.0366 (4)
C15	0.3175 (3)	−0.1104 (2)	0.52758 (14)	0.0429 (4)
H15	0.3302	−0.1848	0.5850	0.052*
C16	0.4145 (3)	−0.1526 (2)	0.44021 (14)	0.0424 (4)
H16	0.4923	−0.2554	0.4381	0.051*
C17	0.3960 (2)	−0.0425 (2)	0.35616 (13)	0.0389 (4)
C18	0.2789 (3)	0.1086 (2)	0.35738 (13)	0.0426 (4)
H18	0.2666	0.1819	0.2995	0.051*
C19	0.1797 (3)	0.1509 (2)	0.44496 (13)	0.0418 (4)
H19	0.0990	0.2523	0.4461	0.050*
N1	−0.1789 (2)	0.52477 (18)	0.92420 (11)	0.0400 (3)
N2	0.1045 (2)	0.07406 (19)	0.62338 (12)	0.0440 (4)
O1	0.10713 (17)	0.37852 (16)	0.89603 (10)	0.0427 (3)
O2	−0.01219 (16)	0.48646 (14)	0.69475 (9)	0.0378 (3)
O3	0.17429 (19)	0.42333 (17)	0.56122 (10)	0.0513 (3)
O4	−0.18764 (17)	0.12567 (14)	0.90801 (9)	0.0405 (3)
O5	−0.04501 (18)	−0.05806 (15)	0.80338 (10)	0.0458 (3)
Br1	0.53764 (3)	−0.10026 (3)	0.237127 (14)	0.05583 (10)
H1A	−0.171 (3)	0.566 (3)	0.9820 (18)	0.067*
H2A	0.077 (3)	−0.004 (3)	0.6630 (19)	0.067*

	U11	U22	U33	U12	U13	U23
C1	0.0486 (12)	0.0401 (10)	0.0558 (12)	−0.0017 (9)	0.0012 (10)	−0.0043 (9)
C2	0.0434 (12)	0.0434 (11)	0.0796 (17)	−0.0040 (9)	−0.0056 (11)	0.0091 (11)
C3	0.0466 (12)	0.0486 (11)	0.0721 (16)	−0.0154 (9)	−0.0230 (11)	0.0164 (11)
C4	0.0535 (12)	0.0409 (10)	0.0489 (11)	−0.0160 (9)	−0.0179 (9)	0.0048 (8)
C5	0.0427 (10)	0.0273 (8)	0.0390 (9)	−0.0086 (7)	−0.0089 (8)	0.0025 (7)
C6	0.0418 (10)	0.0294 (8)	0.0403 (9)	−0.0062 (7)	−0.0032 (8)	−0.0003 (7)
C7	0.0426 (10)	0.0303 (8)	0.0296 (8)	−0.0098 (7)	−0.0047 (7)	−0.0048 (6)
C8	0.0411 (9)	0.0319 (8)	0.0280 (8)	−0.0107 (7)	−0.0057 (7)	−0.0025 (6)
C9	0.0434 (10)	0.0384 (9)	0.0314 (8)	−0.0120 (8)	−0.0064 (7)	−0.0039 (7)
C10	0.0407 (9)	0.0334 (8)	0.0296 (8)	−0.0093 (7)	−0.0061 (7)	−0.0054 (6)
C11	0.0398 (9)	0.0312 (8)	0.0289 (8)	−0.0074 (7)	−0.0071 (7)	−0.0045 (6)
C12	0.0368 (9)	0.0335 (8)	0.0307 (8)	−0.0076 (7)	−0.0073 (7)	−0.0029 (6)
C13	0.0698 (14)	0.0489 (11)	0.0409 (11)	−0.0155 (10)	0.0080 (10)	0.0075 (9)
C14	0.0447 (10)	0.0385 (9)	0.0296 (8)	−0.0141 (8)	−0.0013 (7)	−0.0081 (7)
C15	0.0595 (12)	0.0342 (9)	0.0328 (9)	−0.0087 (8)	−0.0039 (8)	−0.0008 (7)
C16	0.0509 (11)	0.0354 (9)	0.0377 (10)	−0.0039 (8)	−0.0019 (8)	−0.0062 (7)
C17	0.0456 (10)	0.0425 (9)	0.0322 (9)	−0.0163 (8)	−0.0016 (7)	−0.0082 (7)
C18	0.0604 (12)	0.0399 (9)	0.0303 (9)	−0.0163 (9)	−0.0104 (8)	0.0000 (7)
C19	0.0538 (11)	0.0357 (9)	0.0360 (9)	−0.0053 (8)	−0.0120 (8)	−0.0060 (7)
N1	0.0453 (9)	0.0400 (8)	0.0351 (8)	−0.0048 (7)	−0.0057 (7)	−0.0123 (6)
N2	0.0628 (11)	0.0354 (8)	0.0331 (8)	−0.0137 (7)	0.0063 (7)	−0.0081 (6)
O1	0.0403 (7)	0.0487 (7)	0.0402 (7)	−0.0053 (6)	−0.0085 (6)	−0.0126 (6)
O2	0.0499 (7)	0.0329 (6)	0.0316 (6)	−0.0140 (5)	−0.0012 (5)	−0.0026 (5)
O3	0.0622 (9)	0.0502 (8)	0.0425 (8)	−0.0225 (7)	0.0098 (7)	−0.0068 (6)
O4	0.0508 (8)	0.0346 (6)	0.0330 (6)	−0.0081 (5)	0.0012 (5)	−0.0020 (5)
O5	0.0613 (9)	0.0318 (6)	0.0423 (7)	−0.0088 (6)	−0.0003 (6)	−0.0056 (5)
Br1	0.06364 (16)	0.06784 (16)	0.03773 (12)	−0.02209 (11)	0.00927 (9)	−0.01359 (9)

C1—C6	1.375 (3)	C11—C12	1.444 (2)
C1—C2	1.386 (3)	C12—O5	1.214 (2)
C1—H1	0.9300	C12—O4	1.338 (2)
C2—C3	1.368 (3)	C13—O4	1.442 (2)
C2—H2	0.9300	C13—H13A	0.9600
C3—C4	1.396 (3)	C13—H13B	0.9600
C3—H3	0.9300	C13—H13C	0.9600
C4—C5	1.372 (3)	C14—C19	1.381 (2)
C4—H4	0.9300	C14—C15	1.389 (3)
C5—C6	1.383 (2)	C14—N2	1.405 (2)
C5—C8	1.501 (3)	C15—C16	1.370 (3)
C6—N1	1.409 (2)	C15—H15	0.9300
C7—O1	1.213 (2)	C16—C17	1.366 (3)
C7—N1	1.336 (2)	C16—H16	0.9300
C7—C8	1.563 (2)	C17—C18	1.375 (3)
C8—O2	1.446 (2)	C17—Br1	1.8962 (19)
C8—C11	1.496 (2)	C18—C19	1.379 (3)
C9—O3	1.185 (2)	C18—H18	0.9300
C9—O2	1.357 (2)	C19—H19	0.9300
C9—C10	1.497 (2)	N1—H1A	0.92 (2)
C10—N2	1.343 (2)	N2—H2A	0.84 (3)
C10—C11	1.356 (2)
C6—C1—C2	116.7 (2)	O5—C12—O4	123.21 (16)
C6—C1—H1	121.7	O5—C12—C11	123.72 (16)
C2—C1—H1	121.7	O4—C12—C11	113.02 (14)
C3—C2—C1	122.0 (2)	O4—C13—H13A	109.5
C3—C2—H2	119.0	O4—C13—H13B	109.5
C1—C2—H2	119.0	H13A—C13—H13B	109.5
C2—C3—C4	120.7 (2)	O4—C13—H13C	109.5
C2—C3—H3	119.6	H13A—C13—H13C	109.5
C4—C3—H3	119.6	H13B—C13—H13C	109.5
C5—C4—C3	117.7 (2)	C19—C14—C15	119.37 (17)
C5—C4—H4	121.1	C19—C14—N2	124.10 (16)
C3—C4—H4	121.1	C15—C14—N2	116.49 (16)
C4—C5—C6	120.74 (18)	C16—C15—C14	120.46 (17)
C4—C5—C8	130.56 (18)	C16—C15—H15	119.8
C6—C5—C8	108.70 (14)	C14—C15—H15	119.8
C1—C6—C5	122.12 (17)	C17—C16—C15	119.54 (17)
C1—C6—N1	128.20 (18)	C17—C16—H16	120.2
C5—C6—N1	109.67 (15)	C15—C16—H16	120.2
O1—C7—N1	128.24 (15)	C16—C17—C18	121.04 (18)
O1—C7—C8	124.32 (15)	C16—C17—Br1	118.82 (14)
N1—C7—C8	107.43 (15)	C18—C17—Br1	120.13 (14)
O2—C8—C11	103.78 (14)	C17—C18—C19	119.60 (16)
O2—C8—C5	110.91 (13)	C17—C18—H18	120.2
C11—C8—C5	118.36 (14)	C19—C18—H18	120.2
O2—C8—C7	106.91 (13)	C18—C19—C14	119.96 (17)
C11—C8—C7	114.63 (13)	C18—C19—H19	120.0
C5—C8—C7	101.94 (14)	C14—C19—H19	120.0
O3—C9—O2	121.60 (16)	C7—N1—C6	112.18 (15)
O3—C9—C10	130.94 (17)	C7—N1—H1A	123.8 (14)
O2—C9—C10	107.37 (15)	C6—N1—H1A	123.9 (14)
N2—C10—C11	125.71 (16)	C10—N2—C14	132.62 (16)
N2—C10—C9	126.41 (17)	C10—N2—H2A	107.5 (17)
C11—C10—C9	107.60 (14)	C14—N2—H2A	119.9 (17)
C10—C11—C12	123.83 (15)	C9—O2—C8	111.32 (13)
C10—C11—C8	109.57 (14)	C12—O4—C13	114.86 (14)
C12—C11—C8	126.35 (15)
C6—C1—C2—C3	−0.2 (3)	C7—C8—C11—C10	−120.97 (16)
C1—C2—C3—C4	−0.3 (3)	O2—C8—C11—C12	169.66 (15)
C2—C3—C4—C5	0.6 (3)	C5—C8—C11—C12	−67.0 (2)
C3—C4—C5—C6	−0.4 (3)	C7—C8—C11—C12	53.4 (2)
C3—C4—C5—C8	179.71 (16)	C10—C11—C12—O5	−1.3 (3)
C2—C1—C6—C5	0.4 (3)	C8—C11—C12—O5	−174.99 (16)
C2—C1—C6—N1	−178.36 (18)	C10—C11—C12—O4	176.09 (15)
C4—C5—C6—C1	−0.1 (3)	C8—C11—C12—O4	2.4 (2)
C8—C5—C6—C1	179.81 (16)	C19—C14—C15—C16	1.3 (3)
C4—C5—C6—N1	178.90 (16)	N2—C14—C15—C16	179.03 (17)
C8—C5—C6—N1	−1.22 (19)	C14—C15—C16—C17	0.3 (3)
C4—C5—C8—O2	68.7 (2)	C15—C16—C17—C18	−1.4 (3)
C6—C5—C8—O2	−111.21 (15)	C15—C16—C17—Br1	177.77 (14)
C4—C5—C8—C11	−51.1 (3)	C16—C17—C18—C19	0.7 (3)
C6—C5—C8—C11	129.05 (16)	Br1—C17—C18—C19	−178.39 (13)
C4—C5—C8—C7	−177.83 (18)	C17—C18—C19—C14	0.9 (3)
C6—C5—C8—C7	2.31 (17)	C15—C14—C19—C18	−1.9 (3)
O1—C7—C8—O2	−65.7 (2)	N2—C14—C19—C18	−179.48 (17)
N1—C7—C8—O2	113.77 (15)	O1—C7—N1—C6	−178.44 (17)
O1—C7—C8—C11	48.8 (2)	C8—C7—N1—C6	2.16 (19)
N1—C7—C8—C11	−131.82 (16)	C1—C6—N1—C7	178.22 (18)
O1—C7—C8—C5	177.89 (16)	C5—C6—N1—C7	−0.7 (2)
N1—C7—C8—C5	−2.69 (17)	C11—C10—N2—C14	176.41 (18)
O3—C9—C10—N2	−2.8 (3)	C9—C10—N2—C14	−10.5 (3)
O2—C9—C10—N2	−179.46 (16)	C19—C14—N2—C10	−33.1 (3)
O3—C9—C10—C11	171.27 (19)	C15—C14—N2—C10	149.3 (2)
O2—C9—C10—C11	−5.36 (18)	O3—C9—O2—C8	−174.71 (15)
N2—C10—C11—C12	5.7 (3)	C10—C9—O2—C8	2.31 (17)
C9—C10—C11—C12	−168.42 (15)	C11—C8—O2—C9	1.26 (17)
N2—C10—C11—C8	−179.68 (17)	C5—C8—O2—C9	−126.86 (14)
C9—C10—C11—C8	6.16 (18)	C7—C8—O2—C9	122.79 (14)
O2—C8—C11—C10	−4.75 (17)	O5—C12—O4—C13	−1.4 (2)
C5—C8—C11—C10	118.62 (17)	C11—C12—O4—C13	−178.89 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O5	0.84 (2)	2.06 (3)	2.773 (3)	143 (2)
N1—H1A···O1i	0.92 (2)	1.96 (2)	2.869 (3)	168 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O5	0.84 (2)	2.06 (3)	2.773 (3)	143 (2)
N1—H1A⋯O1i	0.92 (2)	1.96 (2)	2.869 (3)	168 (2)

Symmetry code: (i) .