Ethyl 6'-amino-5'-cyano-2'-methyl-2-oxospiro-[indoline-3,4'-pyran]-3'-carboxyl-ate.

In the title compound, C(17)H(15)N(3)O(4), the atoms of the spiro pyran ring are nearly planar with a maximum deviation of 0.0188 (14) Å. The benzene and pyrrole rings make a dihedral angle of 5.71 (6)°. The indole system and the pyran ring are oriented at a dihedral angle of 82.94 (3)°. The crystal structure is stabilized by inter-molecular classical and non-classical N-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds.

Related literature

For the indole nucleus, see: da Silva et al. (2001 ▶). For the anti­bacterial and fungicidal activities of indoles, see: Joshi & Chand (1982 ▶). Spiro­oxindole ring systems are found in a number of alkaloids, e.g. horsifiline, spiro­tryprostatin and elacomine, see: Abdel-Rahman et al. (2004 ▶). For our work on the preparation of heterocyclic compounds involving indole derivatives, see: Zhu et al. (2007 ▶).

Experimental

Crystal data

C17H15N3O4

M = 325.32

Monoclinic,

a = 7.7812 (16) Å

b = 19.998 (4) Å

c = 10.044 (2) Å

β = 103.435 (4)°

V = 1520.2 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 153 K

0.60 × 0.30 × 0.24 mm

Data collection

Rigaku Mercury diffractometer

Absorption correction: multi-scan (ABSCOR; Jacobson, 1998 ▶) T min = 0.764, T max = 0.975

14692 measured reflections

2779 independent reflections

2550 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.096

S = 1.14

2779 reflections

228 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; 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 and PLATOn class="Chemical">N.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054075/pv2248sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054075/pv2248Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H15N3O4	F(000) = 680
Mr = 325.32	Dx = 1.421 Mg m−3
Monoclinic, P21/c	Melting point = 511–512 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71070 Å
a = 7.7812 (16) Å	Cell parameters from 5549 reflections
b = 19.998 (4) Å	θ = 3.1–25.3°
c = 10.044 (2) Å	µ = 0.10 mm−1
β = 103.435 (4)°	T = 153 K
V = 1520.2 (6) Å3	Prism, colorless
Z = 4	0.60 × 0.30 × 0.24 mm

Rigaku Mercury diffractometer	2779 independent reflections
Radiation source: fine-focus sealed tube	2550 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 7.31 pixels mm-1	θmax = 25.3°, θmin = 3.2°
ω scans	h = −8→9
Absorption correction: multi-scan (ABSCOR; Jacobson, 1998)	k = −24→24
Tmin = 0.764, Tmax = 0.975	l = −12→11
14692 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0403P)2 + 0.642P] where P = (Fo2 + 2Fc2)/3
2779 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Experimental. Spectroscopic analysis: IR (KBr, n, cm-1): 3480, 3372, 3287, 2191, 1721, 1620, 1474, 1381, 1288, 1211, 1072, 756, 679, 625. 1H NMR (400 MHz, DMSO-d6): 10.39 (s, 1H, NH), 7.13-7.18 (m, 3H, NH2 + ArH), 7.03 (d, J = 10.0 Hz, 1H, ArH), 6.90 (t, J = 10.0 Hz, 1H, ArH), 6.77 (d, J = 10.4 Hz, 1H, ArH), 3.71-3.76 (m, 2H, CH2), 0.75 (t, J = 9.6 Hz, 3H, CH3).

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. 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 > 2sigma(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
O1	−0.02630 (14)	0.40611 (6)	0.47320 (10)	0.0250 (3)
O2	−0.29838 (16)	0.31533 (6)	0.74767 (13)	0.0361 (3)
O3	−0.15237 (13)	0.38754 (5)	0.90531 (10)	0.0210 (3)
O4	0.02295 (14)	0.52209 (5)	0.82365 (11)	0.0220 (3)
N1	0.21452 (16)	0.45913 (6)	0.98355 (12)	0.0198 (3)
H1	0.2470	0.4898	1.0472	0.024*
N2	0.52683 (18)	0.47764 (7)	0.73427 (15)	0.0310 (3)
N3	0.2201 (2)	0.44309 (8)	0.42427 (14)	0.0266 (3)
H3A	0.322 (3)	0.4642 (10)	0.446 (2)	0.039 (6)*
H3B	0.144 (3)	0.4529 (10)	0.343 (2)	0.039 (5)*
C1	−0.1291 (2)	0.38438 (8)	0.56013 (15)	0.0213 (3)
C2	−0.07153 (19)	0.38461 (7)	0.69607 (15)	0.0186 (3)
C3	0.11176 (19)	0.40821 (7)	0.76868 (15)	0.0172 (3)
C4	0.21368 (19)	0.42787 (7)	0.66251 (15)	0.0178 (3)
C5	0.1420 (2)	0.42671 (7)	0.52598 (15)	0.0198 (3)
C6	−0.3046 (2)	0.36409 (10)	0.47479 (18)	0.0324 (4)
H6A	−0.2958	0.3193	0.4374	0.049*
H6B	−0.3417	0.3960	0.3995	0.049*
H6C	−0.3916	0.3637	0.5313	0.049*
C7	−0.18809 (19)	0.35822 (8)	0.78223 (16)	0.0212 (3)
C8	−0.2410 (2)	0.35970 (8)	1.00633 (16)	0.0252 (4)
H8A	−0.3478	0.3347	0.9593	0.030*
H8B	−0.2782	0.3963	1.0598	0.030*
C9	−0.1167 (3)	0.31383 (10)	1.1002 (2)	0.0395 (5)
H9A	−0.0801	0.2778	1.0467	0.059*
H9B	−0.1762	0.2947	1.1673	0.059*
H9C	−0.0125	0.3390	1.1479	0.059*
C10	0.10541 (19)	0.47069 (7)	0.86000 (15)	0.0167 (3)
C11	0.26981 (19)	0.39209 (8)	0.99810 (15)	0.0200 (3)
C12	0.3617 (2)	0.35940 (9)	1.11389 (17)	0.0267 (4)
H12	0.4029	0.3825	1.1979	0.032*
C13	0.3917 (2)	0.29121 (9)	1.10268 (18)	0.0312 (4)
H13	0.4564	0.2675	1.1802	0.037*
C14	0.3292 (2)	0.25720 (9)	0.98083 (19)	0.0311 (4)
H14	0.3489	0.2105	0.9765	0.037*
C15	0.2374 (2)	0.29119 (8)	0.86432 (17)	0.0249 (4)
H15	0.1948	0.2681	0.7805	0.030*
C16	0.21024 (19)	0.35887 (7)	0.87391 (15)	0.0185 (3)
C17	0.3870 (2)	0.45422 (8)	0.70497 (15)	0.0203 (3)

	U11	U22	U33	U12	U13	U23
O1	0.0210 (6)	0.0353 (6)	0.0174 (5)	−0.0048 (5)	0.0020 (4)	0.0002 (5)
O2	0.0352 (7)	0.0357 (7)	0.0425 (7)	−0.0195 (6)	0.0193 (6)	−0.0165 (6)
O3	0.0192 (6)	0.0251 (6)	0.0203 (5)	−0.0058 (4)	0.0075 (4)	−0.0010 (4)
O4	0.0238 (6)	0.0198 (6)	0.0225 (6)	0.0026 (4)	0.0055 (5)	0.0002 (4)
N1	0.0194 (7)	0.0230 (7)	0.0161 (6)	−0.0020 (5)	0.0021 (5)	−0.0028 (5)
N2	0.0216 (8)	0.0377 (8)	0.0339 (8)	−0.0051 (6)	0.0069 (6)	0.0020 (6)
N3	0.0248 (8)	0.0378 (8)	0.0178 (7)	−0.0024 (7)	0.0058 (6)	0.0023 (6)
C1	0.0175 (8)	0.0226 (8)	0.0238 (8)	−0.0010 (6)	0.0049 (6)	−0.0013 (6)
C2	0.0166 (7)	0.0177 (7)	0.0214 (8)	0.0002 (6)	0.0041 (6)	−0.0027 (6)
C3	0.0150 (7)	0.0187 (7)	0.0183 (7)	−0.0005 (6)	0.0050 (6)	0.0001 (6)
C4	0.0163 (7)	0.0191 (7)	0.0185 (7)	0.0008 (6)	0.0050 (6)	−0.0002 (6)
C5	0.0185 (8)	0.0207 (8)	0.0202 (8)	0.0017 (6)	0.0043 (6)	−0.0003 (6)
C6	0.0252 (9)	0.0403 (10)	0.0281 (9)	−0.0073 (8)	−0.0010 (7)	−0.0021 (8)
C7	0.0167 (7)	0.0200 (8)	0.0277 (8)	−0.0009 (6)	0.0069 (6)	−0.0032 (6)
C8	0.0247 (8)	0.0288 (9)	0.0264 (8)	−0.0073 (7)	0.0144 (7)	−0.0009 (7)
C9	0.0426 (11)	0.0362 (10)	0.0437 (11)	−0.0027 (8)	0.0185 (9)	0.0142 (8)
C10	0.0147 (7)	0.0199 (8)	0.0166 (7)	−0.0027 (6)	0.0061 (6)	0.0003 (6)
C11	0.0143 (7)	0.0267 (8)	0.0203 (8)	0.0002 (6)	0.0070 (6)	0.0033 (6)
C12	0.0173 (8)	0.0415 (10)	0.0215 (8)	0.0019 (7)	0.0052 (6)	0.0086 (7)
C13	0.0195 (8)	0.0427 (10)	0.0339 (10)	0.0086 (7)	0.0111 (7)	0.0188 (8)
C14	0.0245 (9)	0.0264 (9)	0.0465 (11)	0.0098 (7)	0.0163 (8)	0.0131 (8)
C15	0.0212 (8)	0.0245 (8)	0.0319 (9)	0.0021 (6)	0.0121 (7)	0.0011 (7)
C16	0.0138 (7)	0.0227 (8)	0.0204 (8)	−0.0002 (6)	0.0072 (6)	0.0024 (6)
C17	0.0209 (8)	0.0242 (8)	0.0167 (7)	0.0022 (6)	0.0059 (6)	0.0024 (6)

O1—C5	1.3577 (19)	C4—C17	1.418 (2)
O1—C1	1.3840 (19)	C6—H6A	0.9800
O2—C7	1.2058 (19)	C6—H6B	0.9800
O3—C7	1.3378 (19)	C6—H6C	0.9800
O3—C8	1.4631 (18)	C8—C9	1.497 (3)
O4—C10	1.2218 (18)	C8—H8A	0.9900
N1—C10	1.3508 (19)	C8—H8B	0.9900
N1—C11	1.405 (2)	C9—H9A	0.9800
N1—H1	0.8800	C9—H9B	0.9800
N2—C17	1.158 (2)	C9—H9C	0.9800
N3—C5	1.345 (2)	C11—C12	1.380 (2)
N3—H3A	0.88 (2)	C11—C16	1.394 (2)
N3—H3B	0.91 (2)	C12—C13	1.392 (3)
C1—C2	1.334 (2)	C12—H12	0.9500
C1—C6	1.490 (2)	C13—C14	1.386 (3)
C2—C7	1.488 (2)	C13—H13	0.9500
C2—C3	1.518 (2)	C14—C15	1.397 (2)
C3—C16	1.517 (2)	C14—H14	0.9500
C3—C4	1.521 (2)	C15—C16	1.377 (2)
C3—C10	1.558 (2)	C15—H15	0.9500
C4—C5	1.355 (2)
C5—O1—C1	119.69 (11)	O3—C8—C9	109.26 (13)
C7—O3—C8	116.35 (12)	O3—C8—H8A	109.8
C10—N1—C11	111.76 (12)	C9—C8—H8A	109.8
C10—N1—H1	124.1	O3—C8—H8B	109.8
C11—N1—H1	124.1	C9—C8—H8B	109.8
C5—N3—H3A	118.2 (13)	H8A—C8—H8B	108.3
C5—N3—H3B	114.7 (13)	C8—C9—H9A	109.5
H3A—N3—H3B	118.5 (19)	C8—C9—H9B	109.5
C2—C1—O1	122.60 (13)	H9A—C9—H9B	109.5
C2—C1—C6	129.37 (14)	C8—C9—H9C	109.5
O1—C1—C6	108.01 (13)	H9A—C9—H9C	109.5
C1—C2—C7	119.26 (14)	H9B—C9—H9C	109.5
C1—C2—C3	123.16 (13)	O4—C10—N1	126.37 (14)
C7—C2—C3	117.53 (13)	O4—C10—C3	125.82 (13)
C16—C3—C2	113.49 (12)	N1—C10—C3	107.73 (12)
C16—C3—C4	113.29 (12)	C12—C11—C16	121.85 (15)
C2—C3—C4	109.16 (12)	C12—C11—N1	128.74 (15)
C16—C3—C10	101.03 (12)	C16—C11—N1	109.36 (13)
C2—C3—C10	112.18 (12)	C11—C12—C13	117.36 (16)
C4—C3—C10	107.37 (11)	C11—C12—H12	121.3
C5—C4—C17	116.72 (13)	C13—C12—H12	121.3
C5—C4—C3	123.09 (13)	C14—C13—C12	121.40 (15)
C17—C4—C3	119.97 (13)	C14—C13—H13	119.3
N3—C5—C4	127.76 (14)	C12—C13—H13	119.3
N3—C5—O1	110.01 (13)	C13—C14—C15	120.47 (16)
C4—C5—O1	122.21 (13)	C13—C14—H14	119.8
C1—C6—H6A	109.5	C15—C14—H14	119.8
C1—C6—H6B	109.5	C16—C15—C14	118.46 (16)
H6A—C6—H6B	109.5	C16—C15—H15	120.8
C1—C6—H6C	109.5	C14—C15—H15	120.8
H6A—C6—H6C	109.5	C15—C16—C11	120.43 (14)
H6B—C6—H6C	109.5	C15—C16—C3	130.66 (14)
O2—C7—O3	123.98 (14)	C11—C16—C3	108.82 (13)
O2—C7—C2	125.02 (14)	N2—C17—C4	176.79 (16)
O3—C7—C2	110.98 (12)
C5—O1—C1—C2	2.1 (2)	C3—C2—C7—O3	30.15 (18)
C5—O1—C1—C6	−179.13 (13)	C7—O3—C8—C9	98.97 (16)
O1—C1—C2—C7	−177.92 (13)	C11—N1—C10—O4	172.10 (14)
C6—C1—C2—C7	3.6 (3)	C11—N1—C10—C3	−11.17 (16)
O1—C1—C2—C3	−0.4 (2)	C16—C3—C10—O4	−172.22 (14)
C6—C1—C2—C3	−178.80 (15)	C2—C3—C10—O4	−51.02 (19)
C1—C2—C3—C16	−129.44 (15)	C4—C3—C10—O4	68.90 (18)
C7—C2—C3—C16	48.16 (17)	C16—C3—C10—N1	11.03 (14)
C1—C2—C3—C4	−2.1 (2)	C2—C3—C10—N1	132.23 (13)
C7—C2—C3—C4	175.55 (12)	C4—C3—C10—N1	−107.85 (13)
C1—C2—C3—C10	116.82 (16)	C10—N1—C11—C12	−170.85 (15)
C7—C2—C3—C10	−65.58 (16)	C10—N1—C11—C16	6.45 (17)
C16—C3—C4—C5	130.57 (15)	C16—C11—C12—C13	−0.6 (2)
C2—C3—C4—C5	3.1 (2)	N1—C11—C12—C13	176.36 (14)
C10—C3—C4—C5	−118.77 (15)	C11—C12—C13—C14	−1.1 (2)
C16—C3—C4—C17	−54.99 (18)	C12—C13—C14—C15	1.6 (2)
C2—C3—C4—C17	177.50 (13)	C13—C14—C15—C16	−0.3 (2)
C10—C3—C4—C17	55.67 (17)	C14—C15—C16—C11	−1.4 (2)
C17—C4—C5—N3	5.3 (2)	C14—C15—C16—C3	−177.64 (14)
C3—C4—C5—N3	179.89 (15)	C12—C11—C16—C15	1.9 (2)
C17—C4—C5—O1	−176.31 (13)	N1—C11—C16—C15	−175.60 (13)
C3—C4—C5—O1	−1.7 (2)	C12—C11—C16—C3	178.90 (13)
C1—O1—C5—N3	177.58 (13)	N1—C11—C16—C3	1.38 (16)
C1—O1—C5—C4	−1.1 (2)	C2—C3—C16—C15	49.0 (2)
C8—O3—C7—O2	6.8 (2)	C4—C3—C16—C15	−76.2 (2)
C8—O3—C7—C2	−172.00 (12)	C10—C3—C16—C15	169.28 (15)
C1—C2—C7—O2	29.0 (2)	C2—C3—C16—C11	−127.57 (13)
C3—C2—C7—O2	−148.67 (16)	C4—C3—C16—C11	107.22 (14)
C1—C2—C7—O3	−152.16 (14)	C10—C3—C16—C11	−7.30 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2i	0.88	2.56	3.321 (2)	146
N1—H1···O3ii	0.88	2.64	3.337 (2)	137
N3—H3A···N2iii	0.88 (2)	2.64 (2)	3.223 (2)	124 (2)
N3—H3B···O4iv	0.91 (2)	1.93 (2)	2.841 (2)	177 (2)
C13—H13···O2v	0.95	2.50	3.293 (2)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2i	0.88	2.56	3.321 (2)	146
N1—H1⋯O3ii	0.88	2.64	3.337 (2)	137
N3—H3A⋯N2iii	0.88 (2)	2.64 (2)	3.223 (2)	124 (2)
N3—H3B⋯O4iv	0.91 (2)	1.93 (2)	2.841 (2)	177 (2)
C13—H13⋯O2v	0.95	2.50	3.293 (2)	141

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .