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The title compound, C9H7FN2O4, was isolated during a manual crystallization screen on 5-fluoro­isatin (5-fluoro­indoline-2,3-dione). Hydrogen-bonded ribbons of the oxindole are formed through pairs of N—H...O and O—H...O inter­actions. These ribbons then pack parallel to (092) and (09\overline{2}) such that a herring-bone motif is established.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035283/tk2184sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035283/tk2184Isup2.hkl
Contains datablock I

CCDC reference: 657820

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.038
  • wR factor = 0.101
  • Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.96
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C2 = ... S
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, (I), (Figure 1) was isolated during a manual crystallization screen on 5-fluoroisatin. The crystallization screen was motivated by a wider investigation into the potential polymorphism displayed by the isomeric compounds 7-fluoroisatin and 5-fluoroisatin (Shankland et al., 2007; Mohamed et al., 2007a,b).

The oxindole derivative, (I), resulted from the side reaction of 5-fluoroisatin with the recrystallization solvent, nitromethane. The synthesis of oxindole derivatives of isatins from nitromethane has been previously reported (Conn & Lindwall, 1936).

Hydrogen-bonded ribbons of the oxindole are formed through pairs of N—H···O and O—H···O interactions (Figure 2 and Table 1). These ribbons then pack parallel to (0 9 2) and (0 9 - 2) such that a herringbone motif is established (Figure 3).

Related literature top

5-Fluoroisatin forms sheets through double N—H···O hydrogen bonds and C—H···O interactions (Naumov et al., 2000). The oxindole derivative, (I), resulted from a side reaction between 5-fluoroisatin and nitromethane. The synthesis of oxindole derivatives of isatins from nitromethane has been previously reported (Conn & Lindwall, 1936). The 1,4-dioxane (Shankland et al., 2007) and DMSO (Mohamed et al., 2007a) solvates of 7-fluoroisatin have been prepared, as well as the DMSO solvate of 5-fluoroisatin (Mohamed et al., 2007b).

Experimental top

Single crystals of the title compound were crystallized by slow solvent evaporation of a saturated solution of 5-fluoroisatin in nitromethane.

Refinement top

All H atoms were refined freely so that the C—H distances were in the range 0.939 (16) to 0.981 (16) Å, N—H = 0.802 (19) Å and O—H = 0.83 (2) Å. The (83) reflections present but, which should be systematically absent for the space group P21/c have been omitted from the refinement.

Structure description top

The title compound, (I), (Figure 1) was isolated during a manual crystallization screen on 5-fluoroisatin. The crystallization screen was motivated by a wider investigation into the potential polymorphism displayed by the isomeric compounds 7-fluoroisatin and 5-fluoroisatin (Shankland et al., 2007; Mohamed et al., 2007a,b).

The oxindole derivative, (I), resulted from the side reaction of 5-fluoroisatin with the recrystallization solvent, nitromethane. The synthesis of oxindole derivatives of isatins from nitromethane has been previously reported (Conn & Lindwall, 1936).

Hydrogen-bonded ribbons of the oxindole are formed through pairs of N—H···O and O—H···O interactions (Figure 2 and Table 1). These ribbons then pack parallel to (0 9 2) and (0 9 - 2) such that a herringbone motif is established (Figure 3).

5-Fluoroisatin forms sheets through double N—H···O hydrogen bonds and C—H···O interactions (Naumov et al., 2000). The oxindole derivative, (I), resulted from a side reaction between 5-fluoroisatin and nitromethane. The synthesis of oxindole derivatives of isatins from nitromethane has been previously reported (Conn & Lindwall, 1936). The 1,4-dioxane (Shankland et al., 2007) and DMSO (Mohamed et al., 2007a) solvates of 7-fluoroisatin have been prepared, as well as the DMSO solvate of 5-fluoroisatin (Mohamed et al., 2007b).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 and PLATON (Spek 2003).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I) showing the numbering scheme used. Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms have been omitted for clarity.
[Figure 2] Fig. 2. Illustration of the ribbon motif in (I) showing the hydrogen-bonding interactions as blue dotted lines. C - dark grey, H - light grey, N - blue, O - red, F - green.
[Figure 3] Fig. 3. Packing diagram for (I) showing the stacking of the ribbons. C - dark grey, H - light grey, N - blue, O - red, F - green.
5-Fluoro-3-hydroxy-3-(nitromethyl)-1H-indol-2(3H)-one top
Crystal data top
C9H7FN2O4F(000) = 464
Mr = 226.17Dx = 1.704 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5148 reflections
a = 7.9400 (8) Åθ = 2.6–28.2°
b = 15.7867 (16) ŵ = 0.15 mm1
c = 7.2980 (8) ÅT = 150 K
β = 105.536 (2)°Block, colourless
V = 881.35 (16) Å30.45 × 0.30 × 0.25 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer
2170 independent reflections
Radiation source: fine-focus sealed tube1966 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω rotation with narrow frames scansθmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1010
Tmin = 0.879, Tmax = 1.000k = 2020
7682 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: difference Fourier map
wR(F2) = 0.101All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.056P)2 + 0.3897P]
where P = (Fo2 + 2Fc2)/3
2087 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C9H7FN2O4V = 881.35 (16) Å3
Mr = 226.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.9400 (8) ŵ = 0.15 mm1
b = 15.7867 (16) ÅT = 150 K
c = 7.2980 (8) Å0.45 × 0.30 × 0.25 mm
β = 105.536 (2)°
Data collection top
Bruker SMART APEX
diffractometer
2170 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1966 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 1.000Rint = 0.029
7682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.101All H-atom parameters refined
S = 1.05Δρmax = 0.40 e Å3
2087 reflectionsΔρmin = 0.29 e Å3
173 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
xyzUiso*/Ueq
C10.18906 (15)0.46235 (7)0.87480 (17)0.0181 (2)
C20.32534 (14)0.43472 (7)0.76650 (16)0.0172 (2)
C30.20654 (15)0.40255 (7)0.58143 (16)0.0173 (2)
C40.24608 (15)0.37339 (8)0.41905 (17)0.0197 (2)
H10.365 (2)0.3737 (10)0.402 (2)0.021 (4)*
C50.10726 (16)0.34140 (8)0.27745 (17)0.0204 (3)
C60.06236 (16)0.33844 (8)0.29063 (17)0.0215 (3)
H20.151 (2)0.3143 (11)0.192 (2)0.026 (4)*
C70.10177 (15)0.37019 (8)0.45338 (18)0.0205 (3)
H30.217 (2)0.3701 (11)0.465 (3)0.027 (4)*
C80.03515 (15)0.40167 (7)0.59618 (16)0.0176 (2)
C90.42671 (16)0.36201 (8)0.88774 (17)0.0190 (2)
H60.351 (2)0.3207 (10)0.913 (2)0.020 (4)*
H70.504 (2)0.3841 (10)1.004 (2)0.024 (4)*
N10.02989 (13)0.43790 (7)0.77204 (14)0.0191 (2)
H40.058 (2)0.4466 (12)0.803 (3)0.031 (4)*
N20.54238 (13)0.31607 (7)0.78830 (14)0.0196 (2)
O10.22624 (11)0.49891 (6)1.02900 (13)0.0225 (2)
O20.43033 (12)0.50392 (6)0.74659 (13)0.0223 (2)
H50.534 (3)0.4928 (14)0.799 (3)0.052 (6)*
O30.64238 (16)0.35790 (7)0.72435 (19)0.0416 (3)
O40.53062 (14)0.23967 (6)0.77521 (17)0.0350 (3)
F10.14101 (10)0.31091 (5)0.11608 (11)0.0274 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0173 (5)0.0194 (5)0.0192 (5)0.0016 (4)0.0076 (4)0.0005 (4)
C20.0158 (5)0.0202 (5)0.0170 (5)0.0009 (4)0.0068 (4)0.0017 (4)
C30.0163 (5)0.0188 (5)0.0174 (5)0.0010 (4)0.0055 (4)0.0001 (4)
C40.0188 (5)0.0223 (6)0.0197 (6)0.0002 (4)0.0081 (4)0.0001 (4)
C50.0254 (6)0.0215 (6)0.0163 (5)0.0004 (4)0.0089 (4)0.0017 (4)
C60.0212 (6)0.0232 (6)0.0189 (6)0.0029 (4)0.0035 (4)0.0013 (4)
C70.0165 (5)0.0242 (6)0.0213 (6)0.0014 (4)0.0059 (4)0.0006 (4)
C80.0182 (5)0.0186 (5)0.0175 (5)0.0007 (4)0.0074 (4)0.0007 (4)
C90.0184 (5)0.0224 (6)0.0184 (5)0.0015 (4)0.0084 (4)0.0012 (4)
N10.0148 (5)0.0255 (5)0.0188 (5)0.0012 (4)0.0075 (4)0.0022 (4)
N20.0157 (5)0.0237 (5)0.0192 (5)0.0006 (4)0.0046 (4)0.0026 (4)
O10.0197 (4)0.0291 (5)0.0197 (4)0.0009 (3)0.0068 (3)0.0057 (3)
O20.0175 (4)0.0233 (5)0.0257 (5)0.0046 (3)0.0052 (4)0.0014 (3)
O30.0421 (6)0.0352 (6)0.0622 (8)0.0112 (5)0.0393 (6)0.0132 (5)
O40.0381 (6)0.0212 (5)0.0519 (7)0.0048 (4)0.0226 (5)0.0009 (4)
F10.0308 (4)0.0348 (4)0.0189 (4)0.0034 (3)0.0109 (3)0.0081 (3)
Geometric parameters (Å, º) top
C1—O11.2283 (15)C6—C71.3996 (17)
C1—N11.3420 (15)C6—H20.943 (17)
C1—C21.5634 (15)C7—C81.3813 (17)
C2—O21.4052 (14)C7—H30.940 (18)
C2—C31.5131 (15)C8—N11.4159 (14)
C2—C91.5383 (16)C9—N21.5011 (15)
C3—C41.3835 (16)C9—H60.939 (16)
C3—C81.3936 (16)C9—H70.968 (16)
C4—C51.3885 (17)N1—H40.802 (19)
C4—H10.981 (16)N2—O41.2114 (15)
C5—F11.3636 (13)N2—O31.2177 (15)
C5—C61.3764 (18)O2—H50.83 (2)
O1—C1—N1127.33 (11)C7—C6—H2120.0 (10)
O1—C1—C2124.42 (10)C8—C7—C6117.35 (11)
N1—C1—C2108.24 (10)C8—C7—H3121.3 (11)
O2—C2—C3114.45 (9)C6—C7—H3121.4 (11)
O2—C2—C9113.96 (9)C7—C8—C3122.19 (11)
C3—C2—C9111.60 (10)C7—C8—N1128.38 (11)
O2—C2—C1110.21 (9)C3—C8—N1109.42 (10)
C3—C2—C1101.22 (9)C1—N1—C8111.76 (10)
C9—C2—C1104.11 (9)C1—N1—H4123.7 (13)
C4—C3—C8120.88 (11)C8—N1—H4124.4 (13)
C4—C3—C2130.24 (10)C2—O2—H5109.3 (16)
C8—C3—C2108.82 (10)N2—C9—C2112.09 (9)
C3—C4—C5116.20 (11)N2—C9—H6105.5 (10)
C3—C4—H1123.4 (9)C2—C9—H6111.6 (10)
C5—C4—H1120.3 (9)N2—C9—H7105.5 (10)
F1—C5—C6118.08 (11)C2—C9—H7110.3 (10)
F1—C5—C4118.08 (11)H6—C9—H7111.7 (14)
C6—C5—C4123.84 (11)O4—N2—O3123.65 (11)
C5—C6—C7119.50 (11)O4—N2—C9118.35 (10)
C5—C6—H2120.5 (10)O3—N2—C9118.00 (11)
O1—C1—C2—O252.66 (15)C4—C5—C6—C71.0 (2)
N1—C1—C2—O2128.41 (11)C5—C6—C7—C81.38 (18)
O1—C1—C2—C3174.17 (11)C6—C7—C8—C30.16 (18)
N1—C1—C2—C36.90 (12)C6—C7—C8—N1179.16 (11)
O1—C1—C2—C969.93 (14)C4—C3—C8—C71.57 (18)
N1—C1—C2—C9109.00 (11)C2—C3—C8—C7175.80 (11)
O2—C2—C3—C457.41 (17)C4—C3—C8—N1177.59 (11)
C9—C2—C3—C473.87 (15)C2—C3—C8—N15.04 (13)
C1—C2—C3—C4175.90 (12)O1—C1—N1—C8176.70 (12)
O2—C2—C3—C8125.55 (11)C2—C1—N1—C84.41 (13)
C9—C2—C3—C8103.17 (11)C7—C8—N1—C1179.39 (12)
C1—C2—C3—C87.06 (12)C3—C8—N1—C10.29 (14)
C8—C3—C4—C51.95 (17)O2—C2—C9—N270.42 (12)
C2—C3—C4—C5174.79 (11)C3—C2—C9—N261.11 (12)
C3—C4—C5—F1179.11 (10)C1—C2—C9—N2169.48 (9)
C3—C4—C5—C60.71 (19)C2—C9—N2—O4127.94 (12)
F1—C5—C6—C7179.20 (11)C2—C9—N2—O351.69 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H4···O1i0.802 (19)2.214 (19)2.9700 (13)157.4 (17)
O2—H5···O1ii0.83 (2)1.98 (2)2.7799 (13)161 (2)
Symmetry codes: (i) x, y+1, z+2; (ii) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC9H7FN2O4
Mr226.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)7.9400 (8), 15.7867 (16), 7.2980 (8)
β (°) 105.536 (2)
V3)881.35 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.45 × 0.30 × 0.25
Data collection
DiffractometerBruker SMART APEX
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.879, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
7682, 2170, 1966
Rint0.029
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.101, 1.05
No. of reflections2087
No. of parameters173
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.40, 0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000) and Mercury (Macrae et al., 2006), SHELXL97 and PLATON (Spek 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H4···O1i0.802 (19)2.214 (19)2.9700 (13)157.4 (17)
O2—H5···O1ii0.83 (2)1.98 (2)2.7799 (13)161 (2)
Symmetry codes: (i) x, y+1, z+2; (ii) x+1, y+1, z+2.
 

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