Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035271/tk2183sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035271/tk2183Isup2.hkl |
CCDC reference: 657819
Single crystals of the title solvate were grown from a saturated dimethylsulfoxide solution by slow solvent evaporation at 298 K over a period of approximately one month.
Methyl-H atoms were located from the difference map and refined using a rigid rotor model with C—H = 0.98 Å, and with Uiso(H) = 1.5Ueq(C). All other H atoms were refined freely so that the C—H distances were in the range 0.92 (2) to 0.958 (19) Å and N—H = 0.89 (2) Å. The three reflections with the greatest discrepancies were omitted from the refinement.
The title solvate, (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).
In the crystal structure of (I), molecules of 5-fluoroisatin form chains via C—H···O interactions with the DMSO molecules then linked to one side of these chains by N—H···O hydrogen bonds. In the same way as the 7-fluoroisatin DMSO solvate (Mohamed et al., 2007b), ribbons are formed by the interdigitation of the DMSO molecules (Figure 2 and Table 1). The C—H···O interactions for this compound occur using O2 (i.e. the O not adjacent to the N position) whereas the chain formed by 7-fluoroisatin DMSO (Mohamed et al., 2007b) uses O1. Viewing down the a axis, these ribbons can be seen to form planes parallel to (0 - 1 1) with separations of 2.38 Å and 3.49 Å where the DMSO molecules interdigitate (Figure 3).
7-Fluoroisatin is reported to be a suitable starting material for the preparation of 7-substituted-2-indolinones, a class of compounds which are understood to display anti-convulsant activity in animals (Canas-Rodriguez & Leeming, 1972). 5-Fluoroisatin forms sheets through double N—H···O hydrogen bonds and C—H···O interactions (Naumov et al., 2000). The 1,4-dioxane (Shankland et al., 2007) and DMSO (Mohamed et al., 2007a) solvates of 7-fluoroisatin have also been prepared, as well as the oxindole derivative 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).
C10H10FNO3S | Z = 2 |
Mr = 243.25 | F(000) = 252 |
Triclinic, P1 | Dx = 1.513 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2828 (13) Å | Cell parameters from 3349 reflections |
b = 8.3702 (13) Å | θ = 2.6–28.3° |
c = 8.7613 (14) Å | µ = 0.31 mm−1 |
α = 91.326 (2)° | T = 150 K |
β = 117.099 (2)° | Block, orange |
γ = 97.337 (2)° | 0.79 × 0.47 × 0.22 mm |
V = 534.02 (15) Å3 |
Bruker SMART APEX diffractometer | 2429 independent reflections |
Radiation source: fine-focus sealed tube | 2282 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω rotation with narrow frames scans | θmax = 28.3°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
Tmin = 0.871, Tmax = 1.000 | k = −11→11 |
4674 measured reflections | l = −11→11 |
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)] = 0.032 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0489P)2 + 0.1972P] where P = (Fo2 + 2Fc2)/3 |
2426 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C10H10FNO3S | γ = 97.337 (2)° |
Mr = 243.25 | V = 534.02 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2828 (13) Å | Mo Kα radiation |
b = 8.3702 (13) Å | µ = 0.31 mm−1 |
c = 8.7613 (14) Å | T = 150 K |
α = 91.326 (2)° | 0.79 × 0.47 × 0.22 mm |
β = 117.099 (2)° |
Bruker SMART APEX diffractometer | 2429 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2282 reflections with I > 2σ(I) |
Tmin = 0.871, Tmax = 1.000 | Rint = 0.025 |
4674 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.38 e Å−3 |
2426 reflections | Δρmin = −0.24 e Å−3 |
163 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 | 0.27263 (19) | 0.28862 (15) | 0.48470 (17) | 0.0240 (3) | |
C2 | 0.20213 (18) | 0.15613 (15) | 0.33047 (17) | 0.0216 (3) | |
C3 | 0.36806 (17) | 0.12356 (15) | 0.32246 (16) | 0.0195 (2) | |
C4 | 0.39226 (19) | 0.01360 (16) | 0.21618 (17) | 0.0239 (3) | |
H1 | 0.293 (3) | −0.059 (2) | 0.128 (2) | 0.036 (5)* | |
C5 | 0.5705 (2) | 0.01559 (18) | 0.24401 (18) | 0.0274 (3) | |
C6 | 0.71742 (19) | 0.12245 (19) | 0.36432 (19) | 0.0300 (3) | |
H2 | 0.831 (3) | 0.116 (2) | 0.372 (2) | 0.041 (5)* | |
C7 | 0.69151 (18) | 0.23337 (18) | 0.46907 (18) | 0.0273 (3) | |
H3 | 0.788 (3) | 0.309 (2) | 0.551 (2) | 0.039 (5)* | |
C8 | 0.51515 (17) | 0.22925 (15) | 0.44893 (16) | 0.0206 (2) | |
N1 | 0.45677 (16) | 0.32363 (13) | 0.54376 (14) | 0.0239 (2) | |
H4 | 0.533 (3) | 0.393 (2) | 0.635 (2) | 0.038 (5)* | |
O1 | 0.17722 (16) | 0.34426 (13) | 0.53751 (14) | 0.0355 (3) | |
O2 | 0.04277 (13) | 0.10042 (12) | 0.24154 (14) | 0.0305 (2) | |
F1 | 0.60203 (14) | −0.09251 (12) | 0.14601 (12) | 0.0407 (2) | |
C9 | 0.7818 (2) | 0.41521 (18) | 1.11959 (19) | 0.0347 (3) | |
H9A | 0.6925 | 0.3163 | 1.0666 | 0.052* | |
H9B | 0.7853 | 0.4489 | 1.2291 | 0.052* | |
H9C | 0.9036 | 0.3944 | 1.1405 | 0.052* | |
C10 | 0.90882 (19) | 0.72168 (17) | 1.10596 (17) | 0.0277 (3) | |
H10A | 1.0222 | 0.6799 | 1.1285 | 0.042* | |
H10B | 0.9092 | 0.7493 | 1.2154 | 0.042* | |
H10C | 0.9011 | 0.8186 | 1.0438 | 0.042* | |
O3 | 0.73930 (14) | 0.52031 (12) | 0.82378 (12) | 0.0277 (2) | |
S1 | 0.71618 (4) | 0.57126 (4) | 0.97903 (4) | 0.02225 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0314 (7) | 0.0205 (6) | 0.0234 (6) | 0.0050 (5) | 0.0153 (5) | 0.0022 (5) |
C2 | 0.0245 (6) | 0.0186 (6) | 0.0260 (6) | 0.0034 (5) | 0.0154 (5) | 0.0009 (5) |
C3 | 0.0205 (6) | 0.0187 (5) | 0.0216 (6) | 0.0034 (4) | 0.0115 (5) | 0.0032 (4) |
C4 | 0.0263 (6) | 0.0224 (6) | 0.0259 (6) | 0.0050 (5) | 0.0143 (5) | 0.0012 (5) |
C5 | 0.0341 (7) | 0.0315 (7) | 0.0289 (7) | 0.0153 (6) | 0.0223 (6) | 0.0093 (5) |
C6 | 0.0213 (6) | 0.0432 (8) | 0.0329 (7) | 0.0117 (6) | 0.0164 (6) | 0.0171 (6) |
C7 | 0.0195 (6) | 0.0331 (7) | 0.0248 (6) | 0.0002 (5) | 0.0070 (5) | 0.0087 (5) |
C8 | 0.0228 (6) | 0.0204 (6) | 0.0185 (6) | 0.0032 (5) | 0.0094 (5) | 0.0056 (4) |
N1 | 0.0288 (6) | 0.0209 (5) | 0.0188 (5) | 0.0009 (4) | 0.0093 (4) | −0.0016 (4) |
O1 | 0.0441 (6) | 0.0347 (6) | 0.0374 (6) | 0.0116 (5) | 0.0261 (5) | −0.0027 (4) |
O2 | 0.0217 (5) | 0.0288 (5) | 0.0409 (6) | −0.0011 (4) | 0.0161 (4) | −0.0056 (4) |
F1 | 0.0485 (6) | 0.0484 (6) | 0.0435 (5) | 0.0244 (4) | 0.0325 (5) | 0.0054 (4) |
C9 | 0.0532 (9) | 0.0262 (7) | 0.0314 (7) | 0.0078 (6) | 0.0247 (7) | 0.0061 (6) |
C10 | 0.0280 (7) | 0.0254 (7) | 0.0241 (6) | −0.0001 (5) | 0.0086 (5) | −0.0044 (5) |
O3 | 0.0303 (5) | 0.0305 (5) | 0.0186 (4) | 0.0033 (4) | 0.0088 (4) | −0.0030 (4) |
S1 | 0.01999 (17) | 0.02330 (18) | 0.02206 (17) | 0.00339 (12) | 0.00868 (13) | −0.00185 (12) |
C1—O1 | 1.2135 (16) | C7—C8 | 1.3851 (18) |
C1—N1 | 1.3563 (18) | C7—H3 | 0.94 (2) |
C1—C2 | 1.5630 (18) | C8—N1 | 1.4076 (16) |
C2—O2 | 1.2066 (16) | N1—H4 | 0.89 (2) |
C2—C3 | 1.4666 (17) | C9—S1 | 1.7787 (15) |
C3—C4 | 1.3899 (17) | C9—H9A | 0.9800 |
C3—C8 | 1.3943 (18) | C9—H9B | 0.9800 |
C4—C5 | 1.3805 (19) | C9—H9C | 0.9800 |
C4—H1 | 0.958 (19) | C10—S1 | 1.7814 (13) |
C5—F1 | 1.3610 (15) | C10—H10A | 0.9800 |
C5—C6 | 1.379 (2) | C10—H10B | 0.9800 |
C6—C7 | 1.393 (2) | C10—H10C | 0.9800 |
C6—H2 | 0.92 (2) | O3—S1 | 1.5166 (10) |
O1—C1—N1 | 128.94 (13) | C7—C8—C3 | 121.03 (12) |
O1—C1—C2 | 125.24 (13) | C7—C8—N1 | 127.83 (12) |
N1—C1—C2 | 105.82 (10) | C3—C8—N1 | 111.14 (11) |
O2—C2—C3 | 130.81 (12) | C1—N1—C8 | 111.19 (11) |
O2—C2—C1 | 124.37 (11) | C1—N1—H4 | 125.1 (12) |
C3—C2—C1 | 104.81 (11) | C8—N1—H4 | 123.6 (12) |
C4—C3—C8 | 121.86 (12) | S1—C9—H9A | 109.5 |
C4—C3—C2 | 131.19 (12) | S1—C9—H9B | 109.5 |
C8—C3—C2 | 106.95 (11) | H9A—C9—H9B | 109.5 |
C5—C4—C3 | 115.84 (12) | S1—C9—H9C | 109.5 |
C5—C4—H1 | 121.2 (11) | H9A—C9—H9C | 109.5 |
C3—C4—H1 | 123.0 (11) | H9B—C9—H9C | 109.5 |
F1—C5—C6 | 118.51 (12) | S1—C10—H10A | 109.5 |
F1—C5—C4 | 118.10 (13) | S1—C10—H10B | 109.5 |
C6—C5—C4 | 123.39 (13) | H10A—C10—H10B | 109.5 |
C5—C6—C7 | 120.32 (12) | S1—C10—H10C | 109.5 |
C5—C6—H2 | 117.3 (12) | H10A—C10—H10C | 109.5 |
C7—C6—H2 | 122.3 (12) | H10B—C10—H10C | 109.5 |
C8—C7—C6 | 117.46 (13) | O3—S1—C9 | 106.19 (6) |
C8—C7—H3 | 120.1 (12) | O3—S1—C10 | 106.02 (6) |
C6—C7—H3 | 122.4 (12) | C9—S1—C10 | 97.29 (7) |
O1—C1—C2—O2 | 3.8 (2) | C4—C5—C6—C7 | 1.8 (2) |
N1—C1—C2—O2 | −176.78 (13) | C5—C6—C7—C8 | 1.1 (2) |
O1—C1—C2—C3 | −177.15 (13) | C6—C7—C8—C3 | −3.22 (19) |
N1—C1—C2—C3 | 2.24 (13) | C6—C7—C8—N1 | 177.15 (12) |
O2—C2—C3—C4 | −3.7 (2) | C4—C3—C8—C7 | 2.69 (19) |
C1—C2—C3—C4 | 177.36 (13) | C2—C3—C8—C7 | −177.12 (11) |
O2—C2—C3—C8 | 176.07 (14) | C4—C3—C8—N1 | −177.62 (11) |
C1—C2—C3—C8 | −2.86 (13) | C2—C3—C8—N1 | 2.58 (14) |
C8—C3—C4—C5 | 0.11 (19) | O1—C1—N1—C8 | 178.59 (13) |
C2—C3—C4—C5 | 179.86 (13) | C2—C1—N1—C8 | −0.76 (14) |
C3—C4—C5—F1 | 178.45 (11) | C7—C8—N1—C1 | 178.55 (13) |
C3—C4—C5—C6 | −2.3 (2) | C3—C8—N1—C1 | −1.12 (15) |
F1—C5—C6—C7 | −179.01 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H4···O3 | 0.89 (2) | 1.92 (2) | 2.7935 (15) | 167.0 (18) |
C6—H2···O2i | 0.92 (2) | 2.51 (2) | 3.3484 (17) | 152.1 (16) |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C10H10FNO3S |
Mr | 243.25 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 8.2828 (13), 8.3702 (13), 8.7613 (14) |
α, β, γ (°) | 91.326 (2), 117.099 (2), 97.337 (2) |
V (Å3) | 534.02 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.79 × 0.47 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.871, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4674, 2429, 2282 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.087, 1.04 |
No. of reflections | 2426 |
No. of parameters | 163 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.24 |
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···O3 | 0.89 (2) | 1.92 (2) | 2.7935 (15) | 167.0 (18) |
C6—H2···O2i | 0.92 (2) | 2.51 (2) | 3.3484 (17) | 152.1 (16) |
Symmetry code: (i) x+1, y, z. |
The title solvate, (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).
In the crystal structure of (I), molecules of 5-fluoroisatin form chains via C—H···O interactions with the DMSO molecules then linked to one side of these chains by N—H···O hydrogen bonds. In the same way as the 7-fluoroisatin DMSO solvate (Mohamed et al., 2007b), ribbons are formed by the interdigitation of the DMSO molecules (Figure 2 and Table 1). The C—H···O interactions for this compound occur using O2 (i.e. the O not adjacent to the N position) whereas the chain formed by 7-fluoroisatin DMSO (Mohamed et al., 2007b) uses O1. Viewing down the a axis, these ribbons can be seen to form planes parallel to (0 - 1 1) with separations of 2.38 Å and 3.49 Å where the DMSO molecules interdigitate (Figure 3).