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

Yuan, M.; Wang, Q.; Zhang, Y.; Wang, J.

doi:10.1107/S1600536811034167

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2456

doi:10.1107/S1600536811034167

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

Maosen Yuan,^a ^* Qi Wang,^a Yuejun Zhang ^a and Junru Wang ^a

^aCollege of Science, Northwest A&F University, Yangling 712100, Shannxi Province, People's Republic of China
^*Correspondence e-mail: yuanms@nwsuaf.edu.cn

(Received 16 August 2011; accepted 20 August 2011; online 27 August 2011)

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, P b c a
a = 7.4348 (6) Å
b = 14.0589 (11) Å
c = 15.6401 (16) Å
V = 1634.8 (2) Å³
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[F² > 2σ(F²)] = 0.035
wR(F²) = 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

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) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034167/lh5317sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034167/lh5317Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034167/lh5317Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

	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.

Spiro[cyclopropane-1,3'-indolin]-2'-one top

Crystal data top

C₁₀H₉NO	F(000) = 672
M_r = 159.18	D_x = 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 top

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

Refinement top

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(F_o²) + (0.039P)² + 0.514P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1442 reflections	Δρ_max = 0.15 e Å⁻³
110 parameters	Δρ_min = −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)

Crystal data top

C₁₀H₉NO	V = 1634.8 (2) Å³
M_r = 159.18	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.4348 (6) Å	µ = 0.09 mm⁻¹
b = 14.0589 (11) Å	T = 298 K
c = 15.6401 (16) Å	0.50 × 0.45 × 0.42 mm

Data collection top

Bruker SMART CCD diffractometer	1442 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1024 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.965	R_int = 0.033
7724 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.09	Δρ_max = 0.15 e Å⁻³
1442 reflections	Δρ_min = −0.11 e Å⁻³
110 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₉NO
M_r	159.18
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	7.4348 (6), 14.0589 (11), 15.6401 (16)
V (Å³)	1634.8 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.45 × 0.42

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.959, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	7724, 1442, 1024
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.106, 1.09
No. of reflections	1442
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.11

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) x+1/2, −y+3/2, −z+1.

Acknowledgements

Financial support from the PhD Programs Foundation of the Ministry of Education of China (grant No. 20090204120033) is gratefully acknowledged.

References

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