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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1748.
Published online 2010 June 23. doi:  10.1107/S1600536810023160
PMCID: PMC3006973

1-(Morpholino­meth­yl)indoline-2,3-dione

Abstract

In the title compound, C13H14N2O3, the morpholine ring displays a chair conformation, with the (2,3-dioxoindolin-1-yl)methyl group in an equatorial position. The crystal structure is stabilized by inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the synthesis of isatin-N-Mannich bases, see: Varma & Nobles ((1966 [triangle]). For the bioactivity of isatin derivatives, see: Glover et al. (1980 [triangle], 1988 [triangle]); Maysinger et al. (1980 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1748-scheme1.jpg

Experimental

Crystal data

  • C13H14N2O3
  • M r = 246.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1748-efi1.jpg
  • a = 11.608 (2) Å
  • b = 8.2818 (17) Å
  • c = 12.595 (3) Å
  • β = 100.20 (3)°
  • V = 1191.7 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 K
  • 0.26 × 0.18 × 0.16 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.979, T max = 0.984
  • 7614 measured reflections
  • 3556 independent reflections
  • 2275 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.144
  • S = 0.99
  • 3556 reflections
  • 171 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023160/rz2460sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023160/rz2460Isup2.hkl

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

Acknowledgments

This work was supported financially by two grants from the National Science Foundation of China (No. 50874092) and the Natural Science Research Plan Projects of Shaanxi Science and Technology Department (SJ08B20).

supplementary crystallographic information

Comment

Isatin has draw great attention from being discovered as a component of endogenous monoamine oxidase (MAO) inhibitory activity (tribulin) and subsequently identified as a selective inhibitor of MAO B at low concentrations (Glover et al., 1980, 1988). In the following years, many isatin derivatives, such as isatin hydrazono, isatin Mannich bases and isatin based spiroazetidinones, have also been reported to possess anticonvulsant activity (Maysinger, et al., 1980). Herein we report the synthesis and crystal structure of the title compound.

The X-ray structural analysis confirmed the assignment of the structure from spectroscopic data. The molecular structure of the title compound is depicted in Fig. 1. Geometric parameters of the title compound are in the usual ranges. The morpholin ring displays a typical chair conformation, with the (2,3-dioxoindolin-1-yl)methyl group in equatorial position. In the crystal structure, the molecules are linked into a three-dimensional network by C—H···O hydrogen bonds (Table 1).

Experimental

The title compound was synthesized according the literature method (Varma & Nobles, 1966). Isatin (1 mmol), formaldehyde (1.2 mmol) and morpholin (1.2 mmol) were dissolved in methanol (20 ml). The mixture was refluxed until the disappearance of isatin, 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 = 1:1 v/v), giving the title compound. 1H-NMR (D6—DMSO, 400 MHz): 7.61 (2H, m), 7.15 (1H, t, J = 7.2 Hz), 7.09 (1H, d, J = 8.0 Hz), 4.45 (2H, s), 3.70 (4H, t, J = 4.8 Hz), 2.63 (4H, t, J = 4.8 Hz); MS (EI) m/z: 246 (M+). 20 mg of the title compound was dissolved in 50 ml methanol and the solution was kept at room temperature for 4 d. Slow evaporation of the solvent gave orange single crystals of the title compound suitable for X-ray analysis.

Refinement

The H atoms attached to atom C9 were located in a difference Fourier map and refined freely. All other H atoms were placed at calculated positions and refined as riding, with C—H = 0.93-0.98 Å, and with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
An ORTEP-3 drawing of the title compound, with the atom-numbering scheme and 30% probability displacement ellipsoids.

Crystal data

C13H14N2O3F(000) = 520
Mr = 246.26Dx = 1.373 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7356 reflections
a = 11.608 (2) Åθ = 1.5–25.0°
b = 8.2818 (17) ŵ = 0.10 mm1
c = 12.595 (3) ÅT = 293 K
β = 100.20 (3)°Block, orange
V = 1191.7 (4) Å30.26 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer3556 independent reflections
Radiation source: fine-focus sealed tube2275 reflections with I > 2σ(I)
graphiteRint = 0.021
phi and ω scansθmax = 30.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −15→15
Tmin = 0.979, Tmax = 0.984k = −11→10
7614 measured reflectionsl = −17→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H atoms treated by a mixture of independent and constrained refinement
S = 0.99w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
3556 reflections(Δ/σ)max = 0.039
171 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.22 e Å3

Special details

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)

xyzUiso*/Ueq
N20.91766 (9)0.23385 (12)0.11391 (8)0.0368 (3)
N10.73127 (8)0.33226 (11)0.00535 (8)0.0347 (3)
C70.68098 (9)0.48053 (14)0.03062 (9)0.0313 (3)
O20.59676 (8)0.46330 (13)−0.24949 (7)0.0527 (3)
C100.98088 (11)0.23531 (16)0.02322 (11)0.0414 (3)
H10A0.95910.3302−0.02090.050*
H10B0.96040.1404−0.02120.050*
O31.14402 (7)0.37200 (13)0.13337 (9)0.0564 (3)
O10.73752 (10)0.19019 (12)−0.15122 (8)0.0567 (3)
C60.68346 (10)0.54811 (15)0.13085 (10)0.0379 (3)
H6A0.71920.49570.19340.046*
C80.62332 (10)0.55651 (14)−0.06320 (9)0.0345 (3)
C20.63447 (10)0.45189 (15)−0.15409 (10)0.0377 (3)
C90.79252 (11)0.21364 (15)0.08256 (11)0.0373 (3)
C50.63034 (11)0.69807 (15)0.13481 (11)0.0456 (3)
H5A0.63230.74770.20140.055*
C10.70789 (11)0.30626 (15)−0.10310 (10)0.0385 (3)
C30.56961 (11)0.70484 (16)−0.05764 (11)0.0444 (3)
H3A0.53110.7557−0.11970.053*
C130.95237 (11)0.37262 (17)0.18371 (11)0.0435 (3)
H13A0.91260.36920.24520.052*
H13B0.93030.47180.14430.052*
C40.57469 (12)0.77531 (16)0.04263 (12)0.0495 (4)
H4A0.54030.87570.04810.059*
C121.08328 (12)0.3691 (2)0.22195 (12)0.0540 (4)
H12A1.10650.46160.26800.065*
H12B1.10430.27210.26420.065*
C111.11103 (11)0.23690 (17)0.06581 (12)0.0514 (4)
H11A1.13290.13850.10620.062*
H11B1.15290.23970.00570.062*
H9A0.7745 (10)0.1067 (17)0.0422 (11)0.038 (3)*
H9B0.7566 (11)0.2191 (14)0.1471 (11)0.036 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N20.0360 (5)0.0363 (5)0.0385 (6)0.0006 (4)0.0077 (4)0.0042 (4)
N10.0366 (5)0.0373 (5)0.0306 (5)0.0046 (4)0.0074 (4)−0.0023 (4)
C70.0285 (5)0.0345 (6)0.0319 (6)−0.0018 (4)0.0082 (4)−0.0003 (4)
O20.0613 (6)0.0656 (7)0.0290 (5)−0.0100 (5)0.0018 (4)0.0040 (4)
C100.0420 (7)0.0404 (7)0.0440 (7)0.0003 (5)0.0135 (6)−0.0044 (5)
O30.0414 (5)0.0612 (6)0.0685 (7)−0.0114 (4)0.0150 (5)−0.0142 (5)
O10.0671 (7)0.0587 (6)0.0452 (6)0.0075 (5)0.0125 (5)−0.0178 (5)
C60.0385 (6)0.0456 (7)0.0302 (6)0.0014 (5)0.0073 (5)−0.0019 (5)
C80.0316 (6)0.0402 (6)0.0322 (6)−0.0026 (5)0.0072 (5)0.0032 (5)
C20.0352 (6)0.0475 (7)0.0304 (6)−0.0072 (5)0.0058 (5)0.0025 (5)
C90.0361 (6)0.0362 (6)0.0403 (7)−0.0010 (5)0.0086 (5)0.0055 (5)
C50.0474 (8)0.0460 (7)0.0458 (8)0.0010 (6)0.0146 (6)−0.0114 (6)
C10.0384 (6)0.0449 (7)0.0331 (6)−0.0028 (5)0.0089 (5)−0.0053 (5)
C30.0423 (7)0.0432 (7)0.0474 (8)0.0050 (5)0.0074 (6)0.0115 (6)
C130.0416 (7)0.0487 (7)0.0409 (7)0.0013 (6)0.0092 (6)−0.0057 (6)
C40.0488 (8)0.0391 (7)0.0623 (9)0.0076 (6)0.0145 (7)−0.0014 (6)
C120.0440 (7)0.0652 (9)0.0509 (9)−0.0030 (7)0.0033 (7)−0.0131 (7)
C110.0405 (7)0.0549 (8)0.0611 (9)−0.0008 (6)0.0157 (7)−0.0116 (7)

Geometric parameters (Å, °)

N2—C91.4460 (16)C8—C31.3850 (17)
N2—C131.4596 (16)C8—C21.4597 (17)
N2—C101.4631 (16)C2—C11.5490 (18)
N1—C11.3618 (15)C9—H9A1.024 (14)
N1—C71.4199 (14)C9—H9B0.979 (14)
N1—C91.4736 (15)C5—C41.382 (2)
C7—C61.3765 (16)C5—H5A0.9300
C7—C81.4000 (15)C3—C41.383 (2)
O2—C21.2075 (15)C3—H3A0.9300
C10—C111.5110 (18)C13—C121.5109 (18)
C10—H10A0.9700C13—H13A0.9700
C10—H10B0.9700C13—H13B0.9700
O3—C111.4168 (16)C4—H4A0.9300
O3—C121.4217 (17)C12—H12A0.9700
O1—C11.2180 (14)C12—H12B0.9700
C6—C51.3914 (17)C11—H11A0.9700
C6—H6A0.9300C11—H11B0.9700
C9—N2—C13114.36 (10)C4—C5—C6121.82 (12)
C9—N2—C10113.97 (10)C4—C5—H5A119.1
C13—N2—C10109.92 (10)C6—C5—H5A119.1
C1—N1—C7110.17 (10)O1—C1—N1126.89 (12)
C1—N1—C9122.94 (10)O1—C1—C2126.25 (12)
C7—N1—C9126.73 (10)N1—C1—C2106.86 (10)
C6—C7—C8121.37 (11)C4—C3—C8118.27 (12)
C6—C7—N1127.92 (11)C4—C3—H3A120.9
C8—C7—N1110.71 (10)C8—C3—H3A120.9
N2—C10—C11109.34 (11)N2—C13—C12109.35 (11)
N2—C10—H10A109.8N2—C13—H13A109.8
C11—C10—H10A109.8C12—C13—H13A109.8
N2—C10—H10B109.8N2—C13—H13B109.8
C11—C10—H10B109.8C12—C13—H13B109.8
H10A—C10—H10B108.3H13A—C13—H13B108.3
C11—O3—C12109.81 (11)C3—C4—C5120.66 (13)
C7—C6—C5117.28 (11)C3—C4—H4A119.7
C7—C6—H6A121.4C5—C4—H4A119.7
C5—C6—H6A121.4O3—C12—C13111.11 (12)
C3—C8—C7120.55 (11)O3—C12—H12A109.4
C3—C8—C2132.02 (11)C13—C12—H12A109.4
C7—C8—C2107.44 (10)O3—C12—H12B109.4
O2—C2—C8131.85 (13)C13—C12—H12B109.4
O2—C2—C1123.32 (12)H12A—C12—H12B108.0
C8—C2—C1104.82 (10)O3—C11—C10111.53 (11)
N2—C9—N1116.55 (10)O3—C11—H11A109.3
N2—C9—H9A110.1 (7)C10—C11—H11A109.3
N1—C9—H9A102.5 (7)O3—C11—H11B109.3
N2—C9—H9B108.9 (7)C10—C11—H11B109.3
N1—C9—H9B106.9 (7)H11A—C11—H11B108.0
H9A—C9—H9B111.9 (10)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6A···O1i0.932.473.349 (2)158
C5—H5A···O2ii0.932.523.216 (2)131

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2460).

References

  • Bruker (2001). SMART, SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Glover, V., Halket, J. M., Watkins, P. J., Clow, A., Goodwin, B. L. & Sandler, M. (1988). J. Neurochem.51, 656–659. [PubMed]
  • Glover, V., Reveley, M. A. & Sandler, M. (1980). Biochem. Pharmacol.29, 467–470. [PubMed]
  • Maysinger, D. & Movrin, M. (1980). Arzneim. Forschung.30, 1839–1840. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Varma, R. S. & Nobles, W. L. (1966). J. Heterocycl. Chem.3, 462–465.

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