7-Fluoro­isatin–1,4-dioxane (1/1)

Shankland, K.; Leech, C.K.; Mohamed, S.; Barnett, S.A.; Tocher, D.A.

doi:10.1107/S1600536807035258

7-Fluoroisatin-1,4-dioxane (1/1)

K. Shankland, C. K. Leech, S. Mohamed, S. A. Barnett and D. A. Tocher

The title 1,4-dioxane solvate, C₈H₄FNO₂·C₄H₈O₂, was isolated during a manual crystallization screen on 7-fluoroisatin (7-fluoroindoline-2,3-dione). The 7-fluoroisatin molecule occupies a general position and each of the independent molecules of 1,4-dioxane is disposed about a centre of inversion, with half of each in the asymmetric unit. Hydrogen-bonded ribbons of 7-fluoroisatin are linked by 1,4-dioxane to form sheets parallel to (30 $\overline{1}$ ). Whilst one solvent molecule has an active role in the sheet formation, the other simply fills the cavity formed within the sheet.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035258/tk2181sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035258/tk2181Isup2.hkl Contains datablock I

CCDC reference: 657817

checkCIF report

Key indicators

Single-crystal X-ray study
T = 123 K
Mean (C-C) = 0.002 Å
R factor = 0.039
wR factor = 0.103
Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact  O4     ..  C2      ..       2.81 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.56 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O4     ..  C1      ..       2.96 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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 solvate, (I), (Figure 1) was isolated during a manual crystallization screen on 7-fluoroisatin. The crystallization screen was motivated by a wider investigation into the potential polymorphism displayed by the isomeric compounds 7-fluoroisatin and 5-fluoroisatin (Mohamed et al., 2007a-c).

The crystal structure of (I) is characterized by hydrogen-bonded ribbons of 7-fluoroisatin which are linked into sheets by 1,4-dioxane molecules. Whilst one dioxane molecule uses both oxygen atoms as hydrogen bond acceptors, the second dioxane molecule in the asymmetric unit does not appear to participate in any intermolecular interactions and simply fills the cavities formed within the sheet (Figure 2 and Table 1). The sheets lie parallel to (3 0 - 1) and are separated by 3.84 Å.

Related literature top

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 anticonvulsant activity in animals (Canas-Rodriguez & Leeming, 1972). The dimethylsulfoxide solvates of 7-fluoroisatin (Mohamed et al., 2007a) and 5-fluoroisatin (Mohamed et al., 2007b) have also been prepared, as well as the oxindole derivative of 5-fluoroisatin (Mohamed et al., 2007c).

Experimental top

Single crystals of the title compound were crystallized from a saturated 1,4-dioxane solution by slow evaporation at 278 K over the course of 3 weeks.

Structure description top

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; 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

	Fig. 1. The molecular structures of the components of (I) showing the atomic numbering scheme used. Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms have been omitted for clarity. Each 1,4-dioxane molecule is disposed about a centre of inversion. Symmetry codes: (i) = 1 - x, 1 - y, -z and (ii) = 1 - x, -y, -z.
	Fig. 2. Part of the sheet formed in (I) showing the hydrogen-bonding interactions as blue dotted lines. Colour code: C - dark grey, H - light grey, N - blue, O - red, F - green.
	Fig. 3. Packing diagram showing the stacking of the sheets in (I). Hydrogen-bonding interactions are shown as blue dotted lines. Colour code: C - dark grey, H - light grey, N - blue, O - red, F - green.

7-fluoroindoline-2,3-dione–1,4-dioxane (1/1) top

Crystal data top

C₁₂H₁₂FNO₄	F(000) = 528
M_r = 253.23	D_x = 1.447 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5725 reflections
a = 11.5274 (3) Å	θ = 2.9–28.6°
b = 8.6508 (2) Å	µ = 0.12 mm⁻¹
c = 12.1738 (4) Å	T = 123 K
β = 106.701 (3)°	Plate, yellow
V = 1162.78 (6) Å³	0.35 × 0.24 × 0.06 mm
Z = 4

Data collection top

Oxford Diffraction Gemini diffractometer	2740 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2042 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 16.0 pixels mm^-1	θ_max = 28.7°, θ_min = 2.9°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −11→11
T_min = 0.960, T_max = 0.993	l = −16→16
12479 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: difference Fourier map
wR(F²) = 0.103	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0555P)² + 0.117P] where P = (F_o² + 2F_c²)/3
2740 reflections	(Δ/σ)_max < 0.001
211 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₂H₁₂FNO₄	V = 1162.78 (6) Å³
M_r = 253.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.5274 (3) Å	µ = 0.12 mm⁻¹
b = 8.6508 (2) Å	T = 123 K
c = 12.1738 (4) Å	0.35 × 0.24 × 0.06 mm
β = 106.701 (3)°

Data collection top

Oxford Diffraction Gemini diffractometer	2740 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	2042 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.993	R_int = 0.041
12479 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.103	All H-atom parameters refined
S = 1.04	Δρ_max = 0.30 e Å⁻³
2740 reflections	Δρ_min = −0.16 e Å⁻³
211 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
C1	0.63568 (11)	0.30973 (16)	0.41226 (12)	0.0227 (3)
C2	0.67610 (11)	0.36091 (17)	0.54023 (12)	0.0241 (3)
C3	0.65915 (11)	0.52886 (17)	0.53806 (12)	0.0232 (3)
C4	0.67938 (13)	0.63897 (19)	0.62395 (13)	0.0288 (3)
H1	0.7103 (14)	0.606 (2)	0.7033 (15)	0.037 (5)*
C5	0.65384 (13)	0.79131 (19)	0.59349 (15)	0.0329 (4)
H2	0.6680 (14)	0.867 (2)	0.6539 (15)	0.038 (5)*
C6	0.60940 (13)	0.83359 (18)	0.47911 (15)	0.0318 (4)
H3	0.5924 (15)	0.937 (2)	0.4561 (15)	0.041 (5)*
C7	0.59034 (13)	0.72222 (17)	0.39484 (13)	0.0274 (3)
C8	0.61464 (11)	0.56981 (16)	0.42251 (12)	0.0215 (3)
N1	0.60153 (10)	0.44135 (13)	0.35030 (10)	0.0230 (3)
H4	0.5719 (16)	0.444 (2)	0.2720 (17)	0.048 (5)*
O1	0.63342 (9)	0.17947 (11)	0.37651 (9)	0.0302 (3)
O2	0.71073 (9)	0.27269 (13)	0.61973 (9)	0.0335 (3)
F1	0.54700 (9)	0.76186 (11)	0.28272 (8)	0.0414 (3)
C9	0.38445 (13)	0.47942 (19)	−0.07452 (13)	0.0272 (3)
H9A	0.3873 (14)	0.370 (2)	−0.0935 (13)	0.032 (4)*
H9B	0.3077 (14)	0.5267 (18)	−0.1169 (13)	0.029 (4)*
C10	0.40659 (12)	0.50121 (19)	0.05195 (12)	0.0277 (3)
H10A	0.3476 (14)	0.4418 (17)	0.0791 (13)	0.030 (4)*
H10B	0.4031 (13)	0.610 (2)	0.0727 (13)	0.030 (4)*
O3	0.52419 (8)	0.44245 (11)	0.11257 (8)	0.0262 (2)
C11	0.46557 (12)	0.05248 (19)	0.09413 (13)	0.0270 (3)
H11A	0.4396 (14)	−0.0409 (19)	0.1234 (13)	0.026 (4)*
H11B	0.4563 (13)	0.1403 (18)	0.1444 (13)	0.024 (4)*
C12	0.59628 (12)	0.03656 (18)	0.09507 (13)	0.0272 (3)
H12A	0.6456 (14)	0.0060 (19)	0.1745 (14)	0.031 (4)*
H12B	0.6237 (14)	0.135 (2)	0.0700 (14)	0.031 (4)*
O4	0.60965 (8)	−0.08326 (11)	0.01931 (8)	0.0256 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0195 (6)	0.0247 (7)	0.0234 (7)	−0.0004 (5)	0.0056 (5)	0.0013 (6)
C2	0.0198 (6)	0.0307 (8)	0.0220 (7)	−0.0005 (6)	0.0060 (5)	0.0043 (6)
C3	0.0188 (6)	0.0294 (8)	0.0217 (7)	−0.0007 (5)	0.0065 (5)	0.0007 (6)
C4	0.0257 (7)	0.0387 (9)	0.0233 (8)	−0.0037 (6)	0.0091 (6)	−0.0043 (7)
C5	0.0296 (8)	0.0351 (9)	0.0361 (9)	−0.0053 (6)	0.0126 (7)	−0.0122 (7)
C6	0.0286 (7)	0.0231 (8)	0.0465 (10)	−0.0007 (6)	0.0153 (7)	−0.0011 (7)
C7	0.0258 (7)	0.0293 (8)	0.0266 (8)	0.0013 (6)	0.0066 (6)	0.0053 (6)
C8	0.0181 (6)	0.0249 (7)	0.0216 (7)	−0.0014 (5)	0.0057 (5)	0.0011 (5)
N1	0.0248 (6)	0.0253 (6)	0.0172 (6)	0.0002 (5)	0.0030 (5)	0.0005 (5)
O1	0.0302 (5)	0.0247 (6)	0.0345 (6)	0.0004 (4)	0.0072 (5)	−0.0011 (5)
O2	0.0347 (6)	0.0387 (6)	0.0261 (6)	0.0048 (5)	0.0072 (5)	0.0127 (5)
F1	0.0563 (6)	0.0334 (5)	0.0314 (5)	0.0093 (4)	0.0080 (5)	0.0128 (4)
C9	0.0226 (7)	0.0316 (8)	0.0242 (7)	−0.0019 (6)	0.0017 (6)	0.0027 (6)
C10	0.0232 (7)	0.0348 (8)	0.0244 (8)	0.0010 (6)	0.0057 (6)	0.0020 (7)
O3	0.0246 (5)	0.0316 (6)	0.0196 (5)	−0.0005 (4)	0.0020 (4)	0.0041 (4)
C11	0.0236 (7)	0.0329 (8)	0.0223 (7)	0.0022 (6)	0.0033 (6)	0.0001 (6)
C12	0.0232 (7)	0.0306 (8)	0.0248 (8)	0.0019 (6)	0.0022 (6)	−0.0013 (6)
O4	0.0211 (5)	0.0277 (5)	0.0250 (5)	0.0045 (4)	0.0018 (4)	0.0015 (4)

Geometric parameters (Å, º) top

N1—C1	1.3600 (18)	O3—C9ⁱ	1.4356 (17)
N1—C8	1.3979 (17)	O3—C10	1.4373 (16)
N1—H4	0.92 (2)	C9—O3ⁱ	1.4356 (17)
C1—O1	1.2056 (17)	C9—C10	1.498 (2)
C1—C2	1.5566 (19)	C9—H9A	0.979 (18)
C2—O2	1.2068 (16)	C9—H9B	0.976 (16)
C2—C3	1.465 (2)	C10—H10A	0.983 (16)
C3—C4	1.384 (2)	C10—H10B	0.979 (17)
C3—C8	1.3975 (18)	O4—C12	1.4250 (17)
C4—C5	1.378 (2)	O4—C11ⁱⁱ	1.4288 (17)
C4—H1	0.972 (17)	C11—O4ⁱⁱ	1.4288 (17)
C5—C6	1.388 (2)	C11—C12	1.5097 (19)
C5—H2	0.960 (18)	C11—H11A	0.965 (16)
C6—C7	1.378 (2)	C11—H11B	1.001 (16)
C6—H3	0.944 (18)	C12—H12A	1.006 (16)
C7—F1	1.3558 (17)	C12—H12B	0.990 (17)
C7—C8	1.370 (2)

C1—N1—C8	110.80 (12)	C9ⁱ—O3—C10	109.81 (11)
C1—N1—H4	123.9 (12)	O3ⁱ—C9—C10	110.37 (11)
C8—N1—H4	125.3 (12)	O3ⁱ—C9—H9A	107.6 (9)
O1—C1—N1	127.55 (13)	C10—C9—H9A	110.9 (9)
O1—C1—C2	126.61 (13)	O3ⁱ—C9—H9B	105.6 (9)
N1—C1—C2	105.82 (11)	C10—C9—H9B	110.5 (9)
O2—C2—C3	130.79 (14)	H9A—C9—H9B	111.6 (13)
O2—C2—C1	123.89 (13)	O3—C10—C9	109.89 (12)
C3—C2—C1	105.31 (11)	O3—C10—H10A	106.5 (9)
C4—C3—C8	121.30 (14)	C9—C10—H10A	110.5 (9)
C4—C3—C2	132.56 (13)	O3—C10—H10B	108.1 (9)
C8—C3—C2	106.14 (12)	C9—C10—H10B	112.2 (9)
C5—C4—C3	118.59 (15)	H10A—C10—H10B	109.5 (13)
C5—C4—H1	122.6 (10)	C12—O4—C11ⁱⁱ	109.97 (11)
C3—C4—H1	118.8 (10)	O4ⁱⁱ—C11—C12	110.58 (12)
C4—C5—C6	120.72 (15)	O4ⁱⁱ—C11—H11A	110.3 (9)
C4—C5—H2	117.8 (10)	C12—C11—H11A	109.6 (9)
C6—C5—H2	121.5 (10)	O4ⁱⁱ—C11—H11B	108.0 (8)
C7—C6—C5	119.78 (15)	C12—C11—H11B	110.3 (8)
C7—C6—H3	118.0 (11)	H11A—C11—H11B	108.1 (13)
C5—C6—H3	122.2 (11)	O4—C12—C11	110.78 (12)
F1—C7—C8	118.76 (13)	O4—C12—H12A	107.1 (9)
F1—C7—C6	120.42 (13)	C11—C12—H12A	108.6 (9)
C8—C7—C6	120.82 (14)	O4—C12—H12B	109.0 (10)
C7—C8—C3	118.78 (13)	C11—C12—H12B	109.0 (9)
C7—C8—N1	129.28 (13)	H12A—C12—H12B	112.4 (13)
C3—C8—N1	111.93 (12)

C8—N1—C1—O1	178.58 (13)	C5—C6—C7—C8	0.1 (2)
C8—N1—C1—C2	−0.21 (14)	F1—C7—C8—C3	−179.91 (11)
O1—C1—C2—O2	0.1 (2)	C6—C7—C8—C3	0.1 (2)
N1—C1—C2—O2	178.91 (13)	F1—C7—C8—N1	0.1 (2)
O1—C1—C2—C3	−178.55 (13)	C6—C7—C8—N1	−179.96 (13)
N1—C1—C2—C3	0.25 (13)	C4—C3—C8—C7	−0.33 (19)
O2—C2—C3—C4	1.7 (3)	C2—C3—C8—C7	−179.94 (12)
C1—C2—C3—C4	−179.74 (14)	C4—C3—C8—N1	179.69 (12)
O2—C2—C3—C8	−178.72 (14)	C2—C3—C8—N1	0.07 (14)
C1—C2—C3—C8	−0.19 (13)	C1—N1—C8—C7	−179.89 (14)
C8—C3—C4—C5	0.5 (2)	C1—N1—C8—C3	0.09 (15)
C2—C3—C4—C5	179.97 (14)	C9ⁱ—O3—C10—C9	58.41 (17)
C3—C4—C5—C6	−0.4 (2)	O3ⁱ—C9—C10—O3	−58.75 (17)
C4—C5—C6—C7	0.1 (2)	C11ⁱⁱ—O4—C12—C11	57.46 (17)
C5—C6—C7—F1	−179.98 (13)	O4ⁱⁱ—C11—C12—O4	−57.81 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O3	0.92 (2)	1.86 (2)	2.7727 (15)	175.3 (17)
C4—H1···O2ⁱⁱⁱ	0.972 (17)	2.535 (17)	3.2262 (18)	128.1 (13)

Symmetry code: (iii) −x+3/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂FNO₄
M_r	253.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	11.5274 (3), 8.6508 (2), 12.1738 (4)
β (°)	106.701 (3)
V (Å³)	1162.78 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.24 × 0.06

Data collection
Diffractometer	Oxford Diffraction Gemini
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.960, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	12479, 2740, 2042
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.04
No. of reflections	2740
No. of parameters	211
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.16

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, 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···A	D—H	H···A	D···A	D—H···A
N1—H4···O3	0.92 (2)	1.86 (2)	2.7727 (15)	175.3 (17)
C4—H1···O2ⁱ	0.972 (17)	2.535 (17)	3.2262 (18)	128.1 (13)

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

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7-Fluoro­isatin-1,4-dioxane (1/1)

Supporting information

Key indicators

checkCIF/PLATON results

7-Fluoroisatin-1,4-dioxane (1/1)