3-Hydr­oxy-3-nitro­methyl­indolin-2-one

Tang, Y.; Chen, G.; Zhang, J.; Chen, S.

doi:10.1107/S1600536809039087

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2597

https://doi.org/10.1107/S1600536809039087

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3-Hydroxy-3-nitromethylindolin-2-one

Ying Tang,^a Gang Chen,^a ^* Jie Zhang ^a and Shijun Chen ^a

^aXi'an Shiyou University, College of Chemistry and Chemical Engineering, Dianzi'er Road No. 18 Xi'an 710065, Xi'an, People's Republic of China
^*Correspondence e-mail: tangying78@xsyu.edu.cn

(Received 19 September 2009; accepted 26 September 2009; online 3 October 2009)

In the title compound, C₉H₈N₂O₄, the indolin-2-one ring system is substantially planar [maximum deviation = 0.0353 (15) Å]. In the crystal structure, intermolecular N—H⋯O and O—H⋯O hydrogen bonds are responsible for the formation of a three-dimensional network.

Related literature

For the synthesis of the title compound, see: Imre et al. (2001 ); Long et al. (1978 ).

Experimental

Crystal data

C₉H₈N₂O₄
M_r = 208.17
Orthorhombic, P b c a
a = 10.515 (2) Å
b = 7.3736 (14) Å
c = 23.261 (4) Å
V = 1803.6 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.21 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.941, T_max = 0.961
16322 measured reflections
3807 independent reflections
2098 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.135
S = 1.03
3807 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.13	2.9849 (14)	171
O2—H2A⋯O1ⁱⁱ	0.82	1.93	2.7408 (13)	171
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 (Farrugia, 1997 ) and DIAMOND Brandenburg (1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039087/rz2364sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039087/rz2364Isup2.hkl

checkCIF report

Comment top

3-Hydroxy-3-nitromethyl-1,3-dihydro-indolin-2-one, an important intermediate for the synthesis of natural products, has been synthesized by Henry reaction (Imre et al.,2001; Long et al., 1978). Dehydration of this compound as well as its derivatives provides 3-nitromethylene-1,3-dihydro-indolin-2-one, which is used as a dipolarophile in 1,3-dipolar cycloadditon reactions to synthesize spiro-oxindole compounds. In this paper we report the X-ray crystal structure of the title compound.

The X-ray structural analysis confirmed the assignment of the structure of the title compound from spectroscopic data. The molecular structure is depicted in Fig. 1, and a packing diagram of is depicted in Fig. 2. Geometric parameters of the title compound are in the usual ranges. The indolin-2-one ring system is substantially planar, with a maximum deviation of 0.0353 (15) Å for atom C4. In the crystal structure, intermolecular N–H···O and O–H···O hydrogen bonds (Table 1) are effective in the stabilization of the structure and are responsible for the formation of a three-dimensional network. The O atoms of nitro group are not involved in any hydrogen bond.

Related literature top

For the synthesis of the title compound, see: Imre et al. (2001); Long et al. (1978).

Experimental top

Isatin (1 mmol) was dissolved in nitromethane (20 ml), catalyzed by DBU, until the disappearance of the starting material, as evidenced by thin-layer chromatography. The solvent was removed in vacuo and the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate = 5:1 v/v), giving the title compound. ¹H-NMR (D₆—DMSO, 400 MHz): 10.56 (1H, s), 7.39 (1H, d, J = 7.2 Hz), 7.26 (1H, td, J = 7.6, 1.2 Hz), 6.98 (1H, t, J = 7.6 Hz), 6.85 (1H, d, J = 7.6 Hz), 6.75 (1H, s), 4.99 (2H, dd, J = 12.8, 8.0 Hz); ¹³C-NMR (CDCl₃, 100 MHz): 176.0, 142.6, 130.3, 127.9, 124.7, 121.9, 110.1, 78.5, 72.8; MS (EI) m/z: 208 (M⁺). 30 mg of the solid compound was dissolved in methanol (30 ml) and the solution was kept at room temperature for 4 d. Slow evaporation of the solvent gave colourless single crystals suitable for X-ray analysis.

Structure description top

For the synthesis of the title compound, see: Imre et al. (2001); Long et al. (1978).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND Brandenburg (1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP-3 drawing of the title compound, with the atom-numbering scheme and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed approximately along the b axis. Dashed lines indicate hydrogen bonds.

3-Hydroxy-3-nitromethylindolin-2-one top

Crystal data top

C₉H₈N₂O₄	F(000) = 864
M_r = 208.17	D_x = 1.533 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3122 reflections
a = 10.515 (2) Å	θ = 1.8–34.3°
b = 7.3736 (14) Å	µ = 0.12 mm⁻¹
c = 23.261 (4) Å	T = 293 K
V = 1803.6 (6) Å³	Block, colourless
Z = 8	0.21 × 0.18 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3807 independent reflections
Radiation source: fine-focus sealed tube	2098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 34.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
T_min = 0.941, T_max = 0.961	k = −9→11
16322 measured reflections	l = −28→36

Refinement top

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) = 0.135	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0699P)² + 0.2564P] where P = (F_o² + 2F_c²)/3
3807 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₈N₂O₄	V = 1803.6 (6) Å³
M_r = 208.17	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.515 (2) Å	µ = 0.12 mm⁻¹
b = 7.3736 (14) Å	T = 293 K
c = 23.261 (4) Å	0.21 × 0.18 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3807 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2098 reflections with I > 2σ(I)
T_min = 0.941, T_max = 0.961	R_int = 0.026
16322 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.03	Δρ_max = 0.31 e Å⁻³
3807 reflections	Δρ_min = −0.21 e Å⁻³
136 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.73793 (10)	0.22536 (14)	0.59575 (4)	0.0345 (2)
H1A	0.8121	0.2684	0.5882	0.041*
C7	0.68870 (11)	0.20320 (15)	0.65183 (5)	0.0313 (3)
C8	0.56744 (11)	0.12898 (14)	0.64887 (5)	0.0294 (2)
C2	0.53211 (11)	0.10262 (14)	0.58677 (5)	0.0287 (2)
O1	0.67140 (9)	0.16574 (14)	0.50346 (4)	0.0452 (3)
C3	0.50087 (12)	0.08802 (17)	0.69844 (5)	0.0374 (3)
H3A	0.4196	0.0386	0.6966	0.045*
C9	0.41221 (12)	0.20580 (16)	0.56828 (5)	0.0354 (3)
H9A	0.4059	0.2048	0.5267	0.043*
H9B	0.3377	0.1453	0.5837	0.043*
C6	0.74609 (13)	0.24268 (17)	0.70380 (5)	0.0396 (3)
H6A	0.8264	0.2951	0.7055	0.048*
N2	0.41524 (12)	0.39586 (15)	0.58894 (5)	0.0470 (3)
C5	0.67832 (15)	0.20049 (18)	0.75336 (6)	0.0450 (3)
H5A	0.7145	0.2253	0.7890	0.054*
C4	0.55872 (14)	0.1227 (2)	0.75123 (5)	0.0448 (3)
H4A	0.5167	0.0934	0.7852	0.054*
O3	0.50508 (14)	0.48843 (17)	0.57450 (9)	0.0904 (5)
O4	0.32881 (14)	0.44827 (19)	0.61941 (6)	0.0776 (4)
C1	0.65394 (11)	0.17044 (15)	0.55545 (5)	0.0317 (3)
O2	0.51621 (8)	−0.08414 (11)	0.57414 (4)	0.0391 (2)
H2A	0.4586	−0.0966	0.5507	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0244 (5)	0.0384 (5)	0.0408 (5)	−0.0081 (4)	−0.0017 (4)	0.0000 (4)
C7	0.0299 (6)	0.0267 (5)	0.0372 (6)	0.0003 (4)	−0.0040 (4)	0.0000 (4)
C8	0.0259 (6)	0.0268 (5)	0.0353 (5)	0.0019 (4)	−0.0030 (4)	0.0005 (4)
C2	0.0237 (6)	0.0254 (5)	0.0370 (5)	−0.0008 (4)	−0.0022 (4)	−0.0024 (4)
O1	0.0378 (5)	0.0603 (6)	0.0374 (5)	−0.0092 (4)	0.0023 (4)	−0.0040 (4)
C3	0.0303 (6)	0.0389 (6)	0.0431 (6)	0.0043 (5)	0.0031 (5)	0.0048 (5)
C9	0.0276 (6)	0.0352 (6)	0.0435 (6)	0.0037 (5)	−0.0069 (5)	−0.0055 (5)
C6	0.0370 (7)	0.0356 (6)	0.0463 (6)	−0.0006 (5)	−0.0139 (5)	−0.0037 (5)
N2	0.0474 (7)	0.0366 (6)	0.0569 (7)	0.0135 (5)	−0.0168 (5)	−0.0048 (5)
C5	0.0520 (8)	0.0454 (7)	0.0377 (6)	0.0136 (6)	−0.0120 (5)	−0.0052 (5)
C4	0.0476 (8)	0.0503 (7)	0.0364 (6)	0.0154 (6)	0.0037 (5)	0.0044 (5)
O3	0.0736 (9)	0.0354 (6)	0.1620 (17)	−0.0061 (6)	−0.0100 (9)	0.0024 (7)
O4	0.0866 (10)	0.0763 (8)	0.0700 (8)	0.0389 (7)	−0.0037 (7)	−0.0255 (7)
C1	0.0262 (6)	0.0314 (5)	0.0374 (6)	−0.0017 (4)	−0.0008 (4)	−0.0019 (4)
O2	0.0317 (5)	0.0265 (4)	0.0591 (5)	−0.0010 (3)	−0.0098 (4)	−0.0076 (3)

Geometric parameters (Å, º) top

N1—C1	1.3500 (16)	C3—H3A	0.9300
N1—C7	1.4130 (16)	C9—N2	1.4819 (17)
N1—H1A	0.8600	C9—H9A	0.9700
C7—C6	1.3822 (17)	C9—H9B	0.9700
C7—C8	1.3893 (17)	C6—C5	1.390 (2)
C8—C3	1.3823 (17)	C6—H6A	0.9300
C8—C2	1.5042 (15)	N2—O3	1.2129 (19)
C2—O2	1.4180 (13)	N2—O4	1.2155 (18)
C2—C9	1.5340 (16)	C5—C4	1.383 (2)
C2—C1	1.5563 (16)	C5—H5A	0.9300
O1—C1	1.2237 (14)	C4—H4A	0.9300
C3—C4	1.3940 (19)	O2—H2A	0.8200

C1—N1—C7	111.51 (10)	C2—C9—H9A	109.4
C1—N1—H1A	124.2	N2—C9—H9B	109.4
C7—N1—H1A	124.2	C2—C9—H9B	109.4
C6—C7—C8	121.81 (11)	H9A—C9—H9B	108.0
C6—C7—N1	128.55 (11)	C7—C6—C5	117.02 (12)
C8—C7—N1	109.63 (10)	C7—C6—H6A	121.5
C3—C8—C7	120.63 (11)	C5—C6—H6A	121.5
C3—C8—C2	130.37 (11)	O3—N2—O4	124.39 (14)
C7—C8—C2	108.98 (10)	O3—N2—C9	117.33 (13)
O2—C2—C8	110.71 (9)	O4—N2—C9	118.28 (14)
O2—C2—C9	109.07 (9)	C4—C5—C6	121.94 (12)
C8—C2—C9	114.09 (9)	C4—C5—H5A	119.0
O2—C2—C1	108.19 (9)	C6—C5—H5A	119.0
C8—C2—C1	101.81 (9)	C5—C4—C3	120.29 (12)
C9—C2—C1	112.70 (9)	C5—C4—H4A	119.9
C8—C3—C4	118.28 (12)	C3—C4—H4A	119.9
C8—C3—H3A	120.9	O1—C1—N1	126.62 (11)
C4—C3—H3A	120.9	O1—C1—C2	125.24 (10)
N2—C9—C2	111.13 (9)	N1—C1—C2	108.05 (10)
N2—C9—H9A	109.4	C2—O2—H2A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.13	2.9849 (14)	171
O2—H2A···O1ⁱⁱ	0.82	1.93	2.7408 (13)	171

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

Experimental details

Crystal data
Chemical formula	C₉H₈N₂O₄
M_r	208.17
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.515 (2), 7.3736 (14), 23.261 (4)
V (Å³)	1803.6 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.21 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.941, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	16322, 3807, 2098
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.793

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.135, 1.03
No. of reflections	3807
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.21

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND Brandenburg (1999), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.13	2.9849 (14)	170.8
O2—H2A···O1ⁱⁱ	0.82	1.93	2.7408 (13)	171.1

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

Acknowledgements

This work was supported financially by two grants from the Natural Science Research Plan Projects of Shaanxi Science and Technology Department (SJ08B20) and the Scientific Research Plan Projects of Shaanxi Education Department (08JK413).

References

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