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

In the mol-ecule of the title compound, C(16)H(13)N(3)O(4), the atoms of the spiro pyran ring are nearly planar with a maximum deviation of 0.095 (2) Å. The indole and pyran rings are oriented at a dihedral angle of 87.3 (9)°. In the crystal, mol-ecules are linked by inter-molecular N-H⋯N and N-H⋯O hydrogen bonds.

Related literature

For the indole nucleus, see: Da-Silva et al. (2001 ▶). Compounds carrying the indole moiety exhibit anti­bacterial and fungicidal activity, see: Joshi & Chand (1982 ▶). Spiro­oxindole ring systems are found in a number of alkaloids like 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

C16H13N3O4

M = 311.29

Monoclinic,

a = 15.0260 (15) Å

b = 10.0614 (11) Å

c = 10.4862 (12) Å

β = 105.956 (1)°

V = 1524.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 298 K

0.48 × 0.46 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.954, T max = 0.971

7311 measured reflections

2686 independent reflections

1868 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.127

S = 1.04

2686 reflections

210 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053274/bx2334sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053274/bx2334Isup2.hkl

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

C16H13N3O4	F(000) = 648
Mr = 311.29	Dx = 1.357 Mg m−3
Monoclinic, P21/c	Melting point = 535–536 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.0260 (15) Å	Cell parameters from 2324 reflections
b = 10.0614 (11) Å	θ = 2.5–25.2°
c = 10.4862 (12) Å	µ = 0.10 mm−1
β = 105.956 (1)°	T = 298 K
V = 1524.3 (3) Å3	Block, colorless
Z = 4	0.48 × 0.46 × 0.30 mm

Bruker SMART CCD area-detector diffractometer	2686 independent reflections
Radiation source: fine-focus sealed tube	1868 reflections with I > 2σ(I)
graphite	Rint = 0.032
phi and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.954, Tmax = 0.971	k = −11→11
7311 measured reflections	l = −10→12

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0591P)2 + 0.418P] where P = (Fo2 + 2Fc2)/3
2686 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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
N1	0.19598 (12)	0.37685 (18)	0.79711 (19)	0.0494 (5)
H1	0.1769	0.3191	0.8441	0.059*
N2	0.04118 (12)	0.68602 (18)	0.34455 (18)	0.0465 (5)
H2A	0.0244	0.6167	0.2958	0.056*
H2B	0.0196	0.7628	0.3159	0.056*
N3	0.10939 (15)	0.3376 (2)	0.4093 (2)	0.0615 (6)
O1	0.08135 (10)	0.53203 (14)	0.77799 (14)	0.0455 (4)
O2	0.11839 (10)	0.79566 (13)	0.52291 (15)	0.0471 (4)
O3	0.31267 (10)	0.62292 (17)	0.91261 (15)	0.0547 (4)
O4	0.35592 (12)	0.82091 (18)	0.85572 (19)	0.0712 (6)
C1	0.15256 (14)	0.4927 (2)	0.7562 (2)	0.0384 (5)
C2	0.20453 (13)	0.56267 (19)	0.66513 (19)	0.0349 (5)
C3	0.28596 (13)	0.4696 (2)	0.6779 (2)	0.0407 (5)
C4	0.27590 (15)	0.3614 (2)	0.7541 (2)	0.0464 (6)
C5	0.33919 (17)	0.2580 (2)	0.7802 (3)	0.0633 (7)
H5	0.3323	0.1857	0.8319	0.076*
C6	0.41318 (19)	0.2672 (3)	0.7260 (3)	0.0727 (9)
H6	0.4567	0.1991	0.7413	0.087*
C7	0.42407 (17)	0.3739 (3)	0.6501 (3)	0.0697 (8)
H7	0.4749	0.3774	0.6157	0.084*
C8	0.35978 (15)	0.4768 (3)	0.6242 (2)	0.0528 (6)
H8	0.3665	0.5487	0.5720	0.063*
C9	0.30534 (14)	0.7262 (2)	0.8305 (2)	0.0436 (5)
C10	0.23047 (13)	0.7054 (2)	0.7079 (2)	0.0369 (5)
C11	0.18724 (14)	0.8094 (2)	0.6392 (2)	0.0405 (5)
C12	0.19903 (19)	0.9537 (2)	0.6704 (3)	0.0595 (7)
H12A	0.2337	0.9650	0.7614	0.089*
H12B	0.1393	0.9945	0.6562	0.089*
H12C	0.2316	0.9947	0.6139	0.089*
C13	0.39267 (17)	0.6183 (3)	1.0257 (3)	0.0714 (8)
H13A	0.4466	0.6437	0.9993	0.107*
H13B	0.4006	0.5296	1.0608	0.107*
H13C	0.3843	0.6784	1.0925	0.107*
C14	0.14114 (13)	0.56297 (19)	0.52501 (19)	0.0344 (5)
C15	0.10030 (13)	0.67441 (19)	0.4638 (2)	0.0354 (5)
C16	0.12260 (14)	0.4396 (2)	0.4595 (2)	0.0386 (5)

	U11	U22	U33	U12	U13	U23
N1	0.0516 (11)	0.0375 (11)	0.0572 (13)	−0.0057 (9)	0.0114 (9)	0.0099 (9)
N2	0.0498 (11)	0.0354 (10)	0.0468 (12)	−0.0004 (8)	0.0007 (9)	0.0029 (8)
N3	0.0726 (14)	0.0394 (12)	0.0652 (14)	0.0061 (10)	0.0069 (11)	−0.0167 (10)
O1	0.0468 (9)	0.0417 (9)	0.0516 (10)	−0.0092 (7)	0.0195 (7)	−0.0068 (7)
O2	0.0572 (9)	0.0292 (8)	0.0498 (10)	−0.0015 (7)	0.0064 (8)	−0.0020 (7)
O3	0.0523 (9)	0.0615 (11)	0.0430 (10)	−0.0108 (8)	0.0008 (8)	−0.0016 (8)
O4	0.0635 (11)	0.0758 (13)	0.0673 (12)	−0.0367 (10)	0.0062 (9)	−0.0110 (10)
C1	0.0398 (11)	0.0331 (12)	0.0390 (12)	−0.0088 (9)	0.0053 (9)	−0.0050 (9)
C2	0.0345 (10)	0.0324 (11)	0.0363 (11)	−0.0034 (8)	0.0071 (9)	−0.0007 (9)
C3	0.0358 (11)	0.0414 (13)	0.0401 (12)	−0.0010 (9)	0.0022 (9)	−0.0051 (10)
C4	0.0409 (12)	0.0388 (12)	0.0513 (14)	−0.0006 (10)	−0.0014 (10)	−0.0034 (10)
C5	0.0586 (15)	0.0441 (15)	0.0705 (18)	0.0072 (12)	−0.0105 (14)	0.0011 (12)
C6	0.0519 (15)	0.0648 (19)	0.086 (2)	0.0207 (14)	−0.0061 (15)	−0.0161 (16)
C7	0.0434 (14)	0.085 (2)	0.076 (2)	0.0112 (14)	0.0082 (13)	−0.0167 (17)
C8	0.0405 (12)	0.0635 (16)	0.0523 (15)	0.0028 (11)	0.0091 (11)	−0.0049 (12)
C9	0.0409 (11)	0.0503 (14)	0.0415 (13)	−0.0119 (11)	0.0148 (10)	−0.0103 (11)
C10	0.0387 (11)	0.0376 (12)	0.0365 (12)	−0.0106 (9)	0.0140 (9)	−0.0054 (9)
C11	0.0456 (12)	0.0337 (12)	0.0444 (13)	−0.0115 (9)	0.0162 (10)	−0.0070 (10)
C12	0.0803 (17)	0.0336 (13)	0.0654 (17)	−0.0135 (12)	0.0217 (14)	−0.0105 (11)
C13	0.0563 (16)	0.098 (2)	0.0504 (16)	0.0052 (15)	−0.0013 (13)	−0.0040 (15)
C14	0.0353 (10)	0.0304 (11)	0.0372 (12)	−0.0012 (8)	0.0094 (9)	−0.0029 (9)
C15	0.0363 (11)	0.0303 (11)	0.0400 (13)	−0.0037 (8)	0.0110 (10)	−0.0030 (9)
C16	0.0405 (11)	0.0354 (13)	0.0378 (12)	0.0051 (9)	0.0070 (9)	−0.0005 (10)

N1—C1	1.347 (3)	C4—C5	1.385 (3)
N1—C4	1.403 (3)	C5—C6	1.384 (4)
N1—H1	0.8600	C5—H5	0.9300
N2—C15	1.325 (3)	C6—C7	1.372 (4)
N2—H2A	0.8600	C6—H6	0.9300
N2—H2B	0.8600	C7—C8	1.391 (3)
N3—C16	1.146 (3)	C7—H7	0.9300
O1—C1	1.220 (2)	C8—H8	0.9300
O2—C15	1.361 (2)	C9—C10	1.472 (3)
O2—C11	1.372 (3)	C10—C11	1.333 (3)
O3—C9	1.334 (3)	C11—C12	1.489 (3)
O3—C13	1.439 (3)	C12—H12A	0.9600
O4—C9	1.202 (2)	C12—H12B	0.9600
C1—C2	1.558 (3)	C12—H12C	0.9600
C2—C14	1.515 (3)	C13—H13A	0.9600
C2—C3	1.517 (3)	C13—H13B	0.9600
C2—C10	1.523 (3)	C13—H13C	0.9600
C3—C8	1.377 (3)	C14—C15	1.352 (3)
C3—C4	1.382 (3)	C14—C16	1.409 (3)
C1—N1—C4	112.07 (18)	C3—C8—C7	118.4 (2)
C1—N1—H1	124.0	C3—C8—H8	120.8
C4—N1—H1	124.0	C7—C8—H8	120.8
C15—N2—H2A	120.0	O4—C9—O3	122.7 (2)
C15—N2—H2B	120.0	O4—C9—C10	126.1 (2)
H2A—N2—H2B	120.0	O3—C9—C10	111.16 (18)
C15—O2—C11	120.13 (15)	C11—C10—C9	120.16 (19)
C9—O3—C13	117.34 (19)	C11—C10—C2	122.26 (18)
O1—C1—N1	126.4 (2)	C9—C10—C2	117.58 (18)
O1—C1—C2	125.59 (19)	C10—C11—O2	122.51 (17)
N1—C1—C2	107.80 (18)	C10—C11—C12	129.5 (2)
C14—C2—C3	111.31 (16)	O2—C11—C12	107.98 (18)
C14—C2—C10	108.97 (16)	C11—C12—H12A	109.5
C3—C2—C10	114.92 (16)	C11—C12—H12B	109.5
C14—C2—C1	107.93 (15)	H12A—C12—H12B	109.5
C3—C2—C1	101.24 (16)	C11—C12—H12C	109.5
C10—C2—C1	112.12 (16)	H12A—C12—H12C	109.5
C8—C3—C4	120.4 (2)	H12B—C12—H12C	109.5
C8—C3—C2	130.7 (2)	O3—C13—H13A	109.5
C4—C3—C2	108.86 (18)	O3—C13—H13B	109.5
C3—C4—C5	121.8 (2)	H13A—C13—H13B	109.5
C3—C4—N1	109.75 (18)	O3—C13—H13C	109.5
C5—C4—N1	128.4 (2)	H13A—C13—H13C	109.5
C6—C5—C4	117.0 (3)	H13B—C13—H13C	109.5
C6—C5—H5	121.5	C15—C14—C16	119.74 (18)
C4—C5—H5	121.5	C15—C14—C2	122.94 (17)
C7—C6—C5	121.8 (3)	C16—C14—C2	117.29 (17)
C7—C6—H6	119.1	N2—C15—C14	128.29 (19)
C5—C6—H6	119.1	N2—C15—O2	110.40 (17)
C6—C7—C8	120.6 (3)	C14—C15—O2	121.30 (18)
C6—C7—H7	119.7	N3—C16—C14	178.0 (2)
C8—C7—H7	119.7
C4—N1—C1—O1	179.4 (2)	O3—C9—C10—C11	153.2 (2)
C4—N1—C1—C2	4.4 (2)	O4—C9—C10—C2	152.4 (2)
O1—C1—C2—C14	−63.3 (2)	O3—C9—C10—C2	−26.1 (3)
N1—C1—C2—C14	111.82 (18)	C14—C2—C10—C11	12.2 (3)
O1—C1—C2—C3	179.74 (19)	C3—C2—C10—C11	137.8 (2)
N1—C1—C2—C3	−5.2 (2)	C1—C2—C10—C11	−107.3 (2)
O1—C1—C2—C10	56.7 (3)	C14—C2—C10—C9	−168.64 (16)
N1—C1—C2—C10	−128.16 (18)	C3—C2—C10—C9	−42.9 (2)
C14—C2—C3—C8	67.4 (3)	C1—C2—C10—C9	71.9 (2)
C10—C2—C3—C8	−57.0 (3)	C9—C10—C11—O2	178.62 (18)
C1—C2—C3—C8	−178.1 (2)	C2—C10—C11—O2	−2.2 (3)
C14—C2—C3—C4	−110.22 (19)	C9—C10—C11—C12	−3.6 (3)
C10—C2—C3—C4	125.30 (19)	C2—C10—C11—C12	175.6 (2)
C1—C2—C3—C4	4.3 (2)	C15—O2—C11—C10	−9.0 (3)
C8—C3—C4—C5	0.6 (3)	C15—O2—C11—C12	172.84 (18)
C2—C3—C4—C5	178.6 (2)	C3—C2—C14—C15	−140.8 (2)
C8—C3—C4—N1	−179.97 (19)	C10—C2—C14—C15	−13.0 (3)
C2—C3—C4—N1	−2.0 (2)	C1—C2—C14—C15	108.9 (2)
C1—N1—C4—C3	−1.6 (2)	C3—C2—C14—C16	41.4 (2)
C1—N1—C4—C5	177.7 (2)	C10—C2—C14—C16	169.18 (17)
C3—C4—C5—C6	−0.4 (3)	C1—C2—C14—C16	−68.8 (2)
N1—C4—C5—C6	−179.6 (2)	C16—C14—C15—N2	0.6 (3)
C4—C5—C6—C7	0.3 (4)	C2—C14—C15—N2	−177.10 (18)
C5—C6—C7—C8	−0.6 (4)	C16—C14—C15—O2	−178.37 (18)
C4—C3—C8—C7	−0.8 (3)	C2—C14—C15—O2	3.9 (3)
C2—C3—C8—C7	−178.3 (2)	C11—O2—C15—N2	−171.11 (16)
C6—C7—C8—C3	0.8 (4)	C11—O2—C15—C14	8.0 (3)
C13—O3—C9—O4	−9.1 (3)	C15—C14—C16—N3	176 (100)
C13—O3—C9—C10	169.40 (19)	C2—C14—C16—N3	−6(7)
O4—C9—C10—C11	−28.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3i	0.86	2.09	2.928 (3)	165
N2—H2A···O1ii	0.86	2.17	2.925 (2)	147
N2—H2B···O1iii	0.86	2.34	3.022 (2)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3i	0.86	2.09	2.928 (3)	165
N2—H2A⋯O1ii	0.86	2.17	2.925 (2)	147
N2—H2B⋯O1iii	0.86	2.34	3.022 (2)	136

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