Spiro­[cyclo­propane-1,3′-indolin]-2′-one

Abstract

In the title mol­ecule, C₁₀H₉NO, the dihedral angle between the mean plane of the cyclo­propane ring and the essentially planar [maximum deviation = 0.032 (2) Å] indole ring system is 87.65 (17)°. In the crystal, inter­molecular N—H⋯O hydrogen bonds link mol­ecules into one-dimensional chains along [100].

Related literature

For the applications of indoline-2-one and its derivatives, see: Wang et al. (2011 ▶); Ji et al. (2010 ▶). For a related structure, see: Yong et al. (2007 ▶).

Experimental

Crystal data

• C₁₀H₉NO

• M _r = 159.18

• Orthorhombic,

• a = 7.4348 (6) Å

• b = 14.0589 (11) Å

• c = 15.6401 (16) Å

• V = 1634.8 (2) ų

• Z = 8

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 298 K

• 0.50 × 0.45 × 0.42 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.959, T _max = 0.965

• 7724 measured reflections

• 1442 independent reflections

• 1024 reflections with I > 2σ(I)

• R _int = 0.033

Refinement

• R[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 0.106

• S = 1.09

• 1442 reflections

• 110 parameters

• H-atom parameters constrained

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.11 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811034167/lh5317Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	2.00	2.855 (2)	170

Symmetry code: (i) .

supplementary crystallographic information

Comment

Indoline-2-one and its derivatives have been widely explored as materials for the synthesis of antitumor agents (Wang et al., 2011). Indoline-2-one may also be used as a precursor for synthesizing organic luminescent molecules because of its perfect conformation (Ji et al., 2010). In the course of exploring new electro-optic compounds, we obtained the title compound compound and the crystal structure is reported herein.

The title compound is a spiro-compound and has two substituent ring systems, an indoline-2-one ring and a cyclopropane ring which share the sprio atom C2 (Fig. 1). The dihedral angle between the two rings is 87.65 (17)°. The crystal structure of a similar compound ethyl(1'R,2'R)-2-oxo-1,2-dihydrospiro (cyclopropane-1',3-indole)-2'-carboxylate has been published (Yong et al. 2007). In the crystal, intermolecular N—H···O hydrogen bonds link molecules into one-dimensional chains along [100] (Fig. 2).

Experimental

Indolin-2-one (0.50 g, 3.76 mmol) was dissolved in THF (20 mL) and KOH (0.80 g, 14.3 mmol) was slowly added. After heating the stirred mixture at reflux temperature for 30 min, a solution of 1,2-dibromoethane (1.00 g, 5.35 mmol) in THF was slowly added and the refluxing continued for 2 h. The mixture was then cooled to 333 K and poured into water (200 mL) and was extracted with chloroform and dried over Na₂SO₄. After removing the solvent, the crude product was purified by column chromatography on silica gel, affording the title compound (yield: 0.18 g, 30%). The compound was then dissolved in THF, and colorless crystals were formed on slow evaporation at room temperature over one week.

Refinement

All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.93-0.97 Å and N—H = 0.86 Å and with U_iso(H) = 1.2U_eq(C, N).

Figures

Fig. 1.

The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

Part of the crystal structure with hydrogen bonds shown as dashed lines.

Crystal data

C10H9NO	F(000) = 672
Mr = 159.18	Dx = 1.294 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2492 reflections
a = 7.4348 (6) Å	θ = 2.9–26.3°
b = 14.0589 (11) Å	µ = 0.09 mm−1
c = 15.6401 (16) Å	T = 298 K
V = 1634.8 (2) Å3	Block, colorless
Z = 8	0.50 × 0.45 × 0.42 mm

Data collection

Bruker SMART CCD diffractometer	1442 independent reflections
Radiation source: fine-focus sealed tube	1024 reflections with I > 2σ(I)
graphite	Rint = 0.033
φ and ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→5
Tmin = 0.959, Tmax = 0.965	k = −16→16
7724 measured reflections	l = −18→18

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.106	w = 1/[σ2(Fo2) + (0.039P)2 + 0.514P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
1442 reflections	Δρmax = 0.15 e Å−3
110 parameters	Δρmin = −0.11 e Å−3
0 restraints	Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.59216 (19)	0.65349 (11)	0.54786 (9)	0.0505 (4)
H1	0.6712	0.6798	0.5154	0.061*
O1	0.38643 (18)	0.77529 (9)	0.55038 (10)	0.0683 (5)
C1	0.4374 (2)	0.69564 (13)	0.57235 (12)	0.0485 (5)
C2	0.3453 (2)	0.62839 (13)	0.63111 (11)	0.0457 (5)
C3	0.4605 (2)	0.54356 (12)	0.63342 (11)	0.0445 (5)
C4	0.6083 (2)	0.56211 (12)	0.58160 (11)	0.0440 (4)
C5	0.7419 (3)	0.49602 (16)	0.56891 (13)	0.0617 (6)
H5	0.8403	0.5091	0.5341	0.074*
C6	0.7245 (4)	0.40906 (16)	0.60998 (17)	0.0771 (7)
H6	0.8131	0.3630	0.6029	0.092*
C7	0.5787 (4)	0.38995 (16)	0.66098 (17)	0.0797 (8)
H7	0.5697	0.3311	0.6877	0.096*
C8	0.4454 (3)	0.45660 (14)	0.67318 (14)	0.0651 (6)
H8	0.3468	0.4431	0.7077	0.078*
C9	0.1417 (2)	0.62741 (16)	0.63580 (14)	0.0625 (6)
H9A	0.0765	0.6704	0.5985	0.075*
H9B	0.0831	0.5668	0.6456	0.075*
C10	0.2446 (3)	0.66937 (17)	0.70712 (13)	0.0663 (6)
H10A	0.2490	0.6343	0.7605	0.080*
H10B	0.2424	0.7380	0.7134	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0398 (8)	0.0637 (10)	0.0481 (9)	−0.0077 (7)	0.0010 (7)	0.0114 (7)
O1	0.0568 (9)	0.0588 (9)	0.0892 (11)	−0.0017 (7)	−0.0157 (8)	0.0200 (8)
C1	0.0412 (10)	0.0541 (11)	0.0502 (11)	−0.0046 (8)	−0.0123 (8)	0.0059 (9)
C2	0.0391 (10)	0.0552 (11)	0.0429 (10)	−0.0060 (8)	−0.0023 (8)	0.0017 (8)
C3	0.0453 (10)	0.0490 (10)	0.0394 (10)	−0.0077 (8)	−0.0089 (8)	0.0019 (8)
C4	0.0402 (9)	0.0532 (10)	0.0386 (9)	−0.0024 (8)	−0.0092 (8)	−0.0033 (8)
C5	0.0459 (11)	0.0789 (14)	0.0602 (13)	0.0048 (10)	−0.0129 (9)	−0.0202 (11)
C6	0.0754 (16)	0.0609 (14)	0.0949 (18)	0.0185 (12)	−0.0395 (15)	−0.0222 (13)
C7	0.0890 (19)	0.0562 (13)	0.0939 (18)	−0.0028 (13)	−0.0356 (16)	0.0110 (12)
C8	0.0685 (14)	0.0618 (13)	0.0651 (14)	−0.0127 (11)	−0.0119 (11)	0.0146 (11)
C9	0.0403 (11)	0.0805 (14)	0.0668 (14)	−0.0067 (9)	0.0014 (10)	0.0049 (11)
C10	0.0555 (12)	0.0875 (15)	0.0558 (12)	0.0020 (11)	0.0062 (10)	−0.0075 (11)

Geometric parameters (Å, °)

N1—C1	1.350 (2)	C5—H5	0.9300
N1—C4	1.394 (2)	C6—C7	1.373 (4)
N1—H1	0.8600	C6—H6	0.9300
O1—C1	1.231 (2)	C7—C8	1.377 (3)
C1—C2	1.486 (2)	C7—H7	0.9300
C2—C3	1.469 (2)	C8—H8	0.9300
C2—C9	1.515 (3)	C9—C10	1.476 (3)
C2—C10	1.518 (3)	C9—H9A	0.9700
C3—C8	1.376 (2)	C9—H9B	0.9700
C3—C4	1.390 (2)	C10—H10A	0.9700
C4—C5	1.375 (3)	C10—H10B	0.9700
C5—C6	1.387 (3)
C1—N1—C4	111.75 (15)	C7—C6—C5	121.0 (2)
C1—N1—H1	124.1	C7—C6—H6	119.5
C4—N1—H1	124.1	C5—C6—H6	119.5
O1—C1—N1	125.62 (18)	C6—C7—C8	121.1 (2)
O1—C1—C2	127.56 (18)	C6—C7—H7	119.5
N1—C1—C2	106.81 (15)	C8—C7—H7	119.5
C3—C2—C1	105.25 (15)	C3—C8—C7	118.9 (2)
C3—C2—C9	125.03 (17)	C3—C8—H8	120.6
C1—C2—C9	119.74 (16)	C7—C8—H8	120.6
C3—C2—C10	125.19 (17)	C10—C9—C2	60.99 (13)
C1—C2—C10	118.04 (16)	C10—C9—H9A	117.7
C9—C2—C10	58.22 (13)	C2—C9—H9A	117.7
C8—C3—C4	119.65 (18)	C10—C9—H9B	117.7
C8—C3—C2	133.21 (18)	C2—C9—H9B	117.7
C4—C3—C2	107.12 (15)	H9A—C9—H9B	114.8
C5—C4—C3	121.91 (18)	C9—C10—C2	60.79 (13)
C5—C4—N1	129.09 (18)	C9—C10—H10A	117.7
C3—C4—N1	109.00 (15)	C2—C10—H10A	117.7
C4—C5—C6	117.5 (2)	C9—C10—H10B	117.7
C4—C5—H5	121.3	C2—C10—H10B	117.7
C6—C5—H5	121.3	H10A—C10—H10B	114.8
C4—N1—C1—O1	−178.13 (17)	C8—C3—C4—N1	179.15 (16)
C4—N1—C1—C2	2.87 (19)	C2—C3—C4—N1	0.42 (18)
O1—C1—C2—C3	178.55 (18)	C1—N1—C4—C5	177.34 (17)
N1—C1—C2—C3	−2.47 (18)	C1—N1—C4—C3	−2.14 (19)
O1—C1—C2—C9	31.3 (3)	C3—C4—C5—C6	0.0 (3)
N1—C1—C2—C9	−149.71 (17)	N1—C4—C5—C6	−179.43 (17)
O1—C1—C2—C10	−36.2 (3)	C4—C5—C6—C7	0.3 (3)
N1—C1—C2—C10	142.81 (16)	C5—C6—C7—C8	−0.2 (3)
C1—C2—C3—C8	−177.26 (19)	C4—C3—C8—C7	0.5 (3)
C9—C2—C3—C8	−32.3 (3)	C2—C3—C8—C7	178.80 (19)
C10—C2—C3—C8	40.7 (3)	C6—C7—C8—C3	−0.2 (3)
C1—C2—C3—C4	1.23 (18)	C3—C2—C9—C10	113.2 (2)
C9—C2—C3—C4	146.22 (18)	C1—C2—C9—C10	−106.4 (2)
C10—C2—C3—C4	−140.81 (17)	C3—C2—C10—C9	−112.9 (2)
C8—C3—C4—C5	−0.4 (3)	C1—C2—C10—C9	109.34 (19)
C2—C3—C4—C5	−179.11 (16)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.00	2.855 (2)	170

Symmetry codes: (i) x+1/2, −y+3/2, −z+1.