Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035283/tk2184sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035283/tk2184Isup2.hkl |
CCDC reference: 657820
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (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
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).
Single crystals of the title compound were crystallized by slow solvent evaporation of a saturated solution of 5-fluoroisatin in nitromethane.
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.
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).
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).
C9H7FN2O4 | F(000) = 464 |
Mr = 226.17 | Dx = 1.704 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5148 reflections |
a = 7.9400 (8) Å | θ = 2.6–28.2° |
b = 15.7867 (16) Å | µ = 0.15 mm−1 |
c = 7.2980 (8) Å | T = 150 K |
β = 105.536 (2)° | Block, colourless |
V = 881.35 (16) Å3 | 0.45 × 0.30 × 0.25 mm |
Z = 4 |
Bruker SMART APEX diffractometer | 2170 independent reflections |
Radiation source: fine-focus sealed tube | 1966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω rotation with narrow frames scans | θmax = 28.3°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
Tmin = 0.879, Tmax = 1.000 | k = −20→20 |
7682 measured reflections | l = −9→9 |
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)] = 0.038 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.101 | All 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 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C9H7FN2O4 | V = 881.35 (16) Å3 |
Mr = 226.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.9400 (8) Å | µ = 0.15 mm−1 |
b = 15.7867 (16) Å | T = 150 K |
c = 7.2980 (8) Å | 0.45 × 0.30 × 0.25 mm |
β = 105.536 (2)° |
Bruker SMART APEX diffractometer | 2170 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1966 reflections with I > 2σ(I) |
Tmin = 0.879, Tmax = 1.000 | Rint = 0.029 |
7682 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.101 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.40 e Å−3 |
2087 reflections | Δρmin = −0.29 e Å−3 |
173 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.18906 (15) | 0.46235 (7) | 0.87480 (17) | 0.0181 (2) | |
C2 | 0.32534 (14) | 0.43472 (7) | 0.76650 (16) | 0.0172 (2) | |
C3 | 0.20654 (15) | 0.40255 (7) | 0.58143 (16) | 0.0173 (2) | |
C4 | 0.24608 (15) | 0.37339 (8) | 0.41905 (17) | 0.0197 (2) | |
H1 | 0.365 (2) | 0.3737 (10) | 0.402 (2) | 0.021 (4)* | |
C5 | 0.10726 (16) | 0.34140 (8) | 0.27745 (17) | 0.0204 (3) | |
C6 | −0.06236 (16) | 0.33844 (8) | 0.29063 (17) | 0.0215 (3) | |
H2 | −0.151 (2) | 0.3143 (11) | 0.192 (2) | 0.026 (4)* | |
C7 | −0.10177 (15) | 0.37019 (8) | 0.45338 (18) | 0.0205 (3) | |
H3 | −0.217 (2) | 0.3701 (11) | 0.465 (3) | 0.027 (4)* | |
C8 | 0.03515 (15) | 0.40167 (7) | 0.59618 (16) | 0.0176 (2) | |
C9 | 0.42671 (16) | 0.36201 (8) | 0.88774 (17) | 0.0190 (2) | |
H6 | 0.351 (2) | 0.3207 (10) | 0.913 (2) | 0.020 (4)* | |
H7 | 0.504 (2) | 0.3841 (10) | 1.004 (2) | 0.024 (4)* | |
N1 | 0.02989 (13) | 0.43790 (7) | 0.77204 (14) | 0.0191 (2) | |
H4 | −0.058 (2) | 0.4466 (12) | 0.803 (3) | 0.031 (4)* | |
N2 | 0.54238 (13) | 0.31607 (7) | 0.78830 (14) | 0.0196 (2) | |
O1 | 0.22624 (11) | 0.49891 (6) | 1.02900 (13) | 0.0225 (2) | |
O2 | 0.43033 (12) | 0.50392 (6) | 0.74659 (13) | 0.0223 (2) | |
H5 | 0.534 (3) | 0.4928 (14) | 0.799 (3) | 0.052 (6)* | |
O3 | 0.64238 (16) | 0.35790 (7) | 0.72435 (19) | 0.0416 (3) | |
O4 | 0.53062 (14) | 0.23967 (6) | 0.77521 (17) | 0.0350 (3) | |
F1 | 0.14101 (10) | 0.31091 (5) | 0.11608 (11) | 0.0274 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0173 (5) | 0.0194 (5) | 0.0192 (5) | 0.0016 (4) | 0.0076 (4) | 0.0005 (4) |
C2 | 0.0158 (5) | 0.0202 (5) | 0.0170 (5) | −0.0009 (4) | 0.0068 (4) | −0.0017 (4) |
C3 | 0.0163 (5) | 0.0188 (5) | 0.0174 (5) | −0.0010 (4) | 0.0055 (4) | −0.0001 (4) |
C4 | 0.0188 (5) | 0.0223 (6) | 0.0197 (6) | −0.0002 (4) | 0.0081 (4) | −0.0001 (4) |
C5 | 0.0254 (6) | 0.0215 (6) | 0.0163 (5) | −0.0004 (4) | 0.0089 (4) | −0.0017 (4) |
C6 | 0.0212 (6) | 0.0232 (6) | 0.0189 (6) | −0.0029 (4) | 0.0035 (4) | −0.0013 (4) |
C7 | 0.0165 (5) | 0.0242 (6) | 0.0213 (6) | −0.0014 (4) | 0.0059 (4) | 0.0006 (4) |
C8 | 0.0182 (5) | 0.0186 (5) | 0.0175 (5) | 0.0007 (4) | 0.0074 (4) | 0.0007 (4) |
C9 | 0.0184 (5) | 0.0224 (6) | 0.0184 (5) | 0.0015 (4) | 0.0084 (4) | −0.0012 (4) |
N1 | 0.0148 (5) | 0.0255 (5) | 0.0188 (5) | 0.0012 (4) | 0.0075 (4) | −0.0022 (4) |
N2 | 0.0157 (5) | 0.0237 (5) | 0.0192 (5) | 0.0006 (4) | 0.0046 (4) | −0.0026 (4) |
O1 | 0.0197 (4) | 0.0291 (5) | 0.0197 (4) | 0.0009 (3) | 0.0068 (3) | −0.0057 (3) |
O2 | 0.0175 (4) | 0.0233 (5) | 0.0257 (5) | −0.0046 (3) | 0.0052 (4) | 0.0014 (3) |
O3 | 0.0421 (6) | 0.0352 (6) | 0.0622 (8) | −0.0112 (5) | 0.0393 (6) | −0.0132 (5) |
O4 | 0.0381 (6) | 0.0212 (5) | 0.0519 (7) | 0.0048 (4) | 0.0226 (5) | −0.0009 (4) |
F1 | 0.0308 (4) | 0.0348 (4) | 0.0189 (4) | −0.0034 (3) | 0.0109 (3) | −0.0081 (3) |
C1—O1 | 1.2283 (15) | C6—C7 | 1.3996 (17) |
C1—N1 | 1.3420 (15) | C6—H2 | 0.943 (17) |
C1—C2 | 1.5634 (15) | C7—C8 | 1.3813 (17) |
C2—O2 | 1.4052 (14) | C7—H3 | 0.940 (18) |
C2—C3 | 1.5131 (15) | C8—N1 | 1.4159 (14) |
C2—C9 | 1.5383 (16) | C9—N2 | 1.5011 (15) |
C3—C4 | 1.3835 (16) | C9—H6 | 0.939 (16) |
C3—C8 | 1.3936 (16) | C9—H7 | 0.968 (16) |
C4—C5 | 1.3885 (17) | N1—H4 | 0.802 (19) |
C4—H1 | 0.981 (16) | N2—O4 | 1.2114 (15) |
C5—F1 | 1.3636 (13) | N2—O3 | 1.2177 (15) |
C5—C6 | 1.3764 (18) | O2—H5 | 0.83 (2) |
O1—C1—N1 | 127.33 (11) | C7—C6—H2 | 120.0 (10) |
O1—C1—C2 | 124.42 (10) | C8—C7—C6 | 117.35 (11) |
N1—C1—C2 | 108.24 (10) | C8—C7—H3 | 121.3 (11) |
O2—C2—C3 | 114.45 (9) | C6—C7—H3 | 121.4 (11) |
O2—C2—C9 | 113.96 (9) | C7—C8—C3 | 122.19 (11) |
C3—C2—C9 | 111.60 (10) | C7—C8—N1 | 128.38 (11) |
O2—C2—C1 | 110.21 (9) | C3—C8—N1 | 109.42 (10) |
C3—C2—C1 | 101.22 (9) | C1—N1—C8 | 111.76 (10) |
C9—C2—C1 | 104.11 (9) | C1—N1—H4 | 123.7 (13) |
C4—C3—C8 | 120.88 (11) | C8—N1—H4 | 124.4 (13) |
C4—C3—C2 | 130.24 (10) | C2—O2—H5 | 109.3 (16) |
C8—C3—C2 | 108.82 (10) | N2—C9—C2 | 112.09 (9) |
C3—C4—C5 | 116.20 (11) | N2—C9—H6 | 105.5 (10) |
C3—C4—H1 | 123.4 (9) | C2—C9—H6 | 111.6 (10) |
C5—C4—H1 | 120.3 (9) | N2—C9—H7 | 105.5 (10) |
F1—C5—C6 | 118.08 (11) | C2—C9—H7 | 110.3 (10) |
F1—C5—C4 | 118.08 (11) | H6—C9—H7 | 111.7 (14) |
C6—C5—C4 | 123.84 (11) | O4—N2—O3 | 123.65 (11) |
C5—C6—C7 | 119.50 (11) | O4—N2—C9 | 118.35 (10) |
C5—C6—H2 | 120.5 (10) | O3—N2—C9 | 118.00 (11) |
O1—C1—C2—O2 | −52.66 (15) | C4—C5—C6—C7 | 1.0 (2) |
N1—C1—C2—O2 | 128.41 (11) | C5—C6—C7—C8 | −1.38 (18) |
O1—C1—C2—C3 | −174.17 (11) | C6—C7—C8—C3 | 0.16 (18) |
N1—C1—C2—C3 | 6.90 (12) | C6—C7—C8—N1 | 179.16 (11) |
O1—C1—C2—C9 | 69.93 (14) | C4—C3—C8—C7 | 1.57 (18) |
N1—C1—C2—C9 | −109.00 (11) | C2—C3—C8—C7 | −175.80 (11) |
O2—C2—C3—C4 | 57.41 (17) | C4—C3—C8—N1 | −177.59 (11) |
C9—C2—C3—C4 | −73.87 (15) | C2—C3—C8—N1 | 5.04 (13) |
C1—C2—C3—C4 | 175.90 (12) | O1—C1—N1—C8 | 176.70 (12) |
O2—C2—C3—C8 | −125.55 (11) | C2—C1—N1—C8 | −4.41 (13) |
C9—C2—C3—C8 | 103.17 (11) | C7—C8—N1—C1 | −179.39 (12) |
C1—C2—C3—C8 | −7.06 (12) | C3—C8—N1—C1 | −0.29 (14) |
C8—C3—C4—C5 | −1.95 (17) | O2—C2—C9—N2 | −70.42 (12) |
C2—C3—C4—C5 | 174.79 (11) | C3—C2—C9—N2 | 61.11 (12) |
C3—C4—C5—F1 | −179.11 (10) | C1—C2—C9—N2 | 169.48 (9) |
C3—C4—C5—C6 | 0.71 (19) | C2—C9—N2—O4 | −127.94 (12) |
F1—C5—C6—C7 | −179.20 (11) | C2—C9—N2—O3 | 51.69 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O1i | 0.802 (19) | 2.214 (19) | 2.9700 (13) | 157.4 (17) |
O2—H5···O1ii | 0.83 (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 formula | C9H7FN2O4 |
Mr | 226.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 7.9400 (8), 15.7867 (16), 7.2980 (8) |
β (°) | 105.536 (2) |
V (Å3) | 881.35 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.45 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.879, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7682, 2170, 1966 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.101, 1.05 |
No. of reflections | 2087 |
No. of parameters | 173 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O1i | 0.802 (19) | 2.214 (19) | 2.9700 (13) | 157.4 (17) |
O2—H5···O1ii | 0.83 (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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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).