3-Fluoro-4-nitro­phenyl 4-methyl­benzene­sulfonate

Ang, W.; Luo, Y.-F.; Deng, Y.

doi:10.1107/S1600536811005903

organic compounds

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Volume 67| Part 4| April 2011| Page o750

doi:10.1107/S1600536811005903

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3-Fluoro-4-nitrophenyl 4-methylbenzenesulfonate

Wei Ang,^a You-Fu Luo ^b and Yong Deng ^a ^*

^aKey Laboratory of Drug Targeting and Drug Delivery System of the Education Ministry, Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China, and ^bState Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: dengyongy@sohu.com

(Received 16 December 2010; accepted 17 February 2011; online 2 March 2011)

In the title compound, C₁₃H₁₀FNO₅S, the dihedral angle between the benzene rings is 47.63 (14)°. In the crystal, π–π stacking occurs between nearly parallel benzene rings of adjacent molecules, the centroid–centroid distance being 3.7806 (16) Å. Weak intermolecular C—H⋯O hydrogen bonding is also present in the crystal structure.

Related literature

For related compounds and their biological activity, see: Cho et al. (2003); Marson et al. (2007 ).

Experimental

Crystal data

C₁₃H₁₀FNO₅S
M_r = 311.28
Orthorhombic, P n a 2₁
a = 14.2596 (5) Å
b = 11.4800 (3) Å
c = 8.3602 (2) Å
V = 1368.57 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.979, T_max = 1.0
10802 measured reflections
2251 independent reflections
1855 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.083
S = 1.05
2251 reflections
191 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 752 Friedel pairs
Flack parameter: −0.06 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.55	3.224 (4)	129
Symmetry code: (i) $[-x+1, -y, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005903/xu5126sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005903/xu5126Isup2.hkl

checkCIF report

Comment top

Aryloxyalkanoic acid hydroxyamides are potent inhibitors of histone deacetylase (Marson et al., 2007; Cho et al., 2003). 3-Fluoro-4-nitrophenyl 4-methylbenzenesulfonate is one of the key intermediates to synthesize the aryloxyalkanoic acid hydroxyamides derivatives. We report here its crystal structure. In the title compound (Fig. 1), the dihedral angle between the 3-fluoro-4-nitrophenyl ring and the 4-methylbenzene ring is 47.63 (14)°. In the crystal, intermolecular π-π stacking [centroid–centroid distance = 3.7806 (16) Å] stabilizes the structure (Fig. 2). Weak C—H···O hydrogen bonding is present in the crystal structure (Table 1).

Related literature top

For related compounds and their biological activity, see: Cho et al. (2003); Marson et al. (2007).

Experimental top

To the 3-fluoro-4-nitrophenol (19.10 mmol) in chloroform (20 ml) at 273 K were added pyridine (3.70 ml, 45.84 mmol) dropwise over a period of 20 min and p-toluenesulfonyl chloride (22.92 mmol) in small portions. This reaction mixture was stirred at room temperature for 12 h and diluted with dichloromethane and then 10% aqueous HCl. The separated organic layer was washed with 10% aqueous HCl, water and saturated aqueous NaCl; dried over NaSO4; and concentrated in vacuo. The crude 3-fluoro-4-nitrophenyl 4-methylbenzenesulfonate were purified by recrystallization. Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of ethanol.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The cell packing of the title compound.

3-Fluoro-4-nitrophenyl 4-methylbenzenesulfonate top

Crystal data top

C₁₃H₁₀FNO₅S	F(000) = 640
M_r = 311.28	D_x = 1.511 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2c -2n	Cell parameters from 4234 reflections
a = 14.2596 (5) Å	θ = 2.9–29.1°
b = 11.4800 (3) Å	µ = 0.27 mm⁻¹
c = 8.3602 (2) Å	T = 293 K
V = 1368.57 (7) Å³	Block, colorless
Z = 4	0.30 × 0.30 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2251 independent reflections
Radiation source: fine-focus sealed tube	1855 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 2.9°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	k = −14→14
T_min = 0.979, T_max = 1.0	l = −7→10
10802 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.039P)² + 0.1799P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.025
2251 reflections	Δρ_max = 0.12 e Å⁻³
191 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 752 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (9)

Crystal data top

C₁₃H₁₀FNO₅S	V = 1368.57 (7) Å³
M_r = 311.28	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 14.2596 (5) Å	µ = 0.27 mm⁻¹
b = 11.4800 (3) Å	T = 293 K
c = 8.3602 (2) Å	0.30 × 0.30 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2251 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	1855 reflections with I > 2σ(I)
T_min = 0.979, T_max = 1.0	R_int = 0.025
10802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.12 e Å⁻³
S = 1.05	Δρ_min = −0.23 e Å⁻³
2251 reflections	Absolute structure: Flack (1983), 752 Friedel pairs
191 parameters	Absolute structure parameter: −0.06 (9)
1 restraint

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
S1	0.16636 (4)	0.27076 (5)	0.58998 (10)	0.05567 (19)
F1	0.34171 (15)	−0.14722 (14)	0.6292 (3)	0.1007 (7)
O1	0.56870 (17)	−0.0441 (2)	0.8899 (4)	0.0906 (8)
O2	0.51366 (19)	−0.1649 (2)	0.7187 (3)	0.1041 (9)
O3	0.18775 (13)	0.20401 (17)	0.7566 (2)	0.0574 (5)
O4	0.16341 (14)	0.18606 (19)	0.4665 (3)	0.0675 (6)
O5	0.08578 (12)	0.33777 (18)	0.6260 (3)	0.0788 (7)
N1	0.5080 (2)	−0.0778 (2)	0.7989 (3)	0.0675 (7)
C1	0.4217 (2)	−0.0077 (2)	0.7863 (4)	0.0523 (7)
C2	0.3442 (2)	−0.0442 (2)	0.7026 (4)	0.0601 (8)
C3	0.2660 (2)	0.0248 (2)	0.6906 (4)	0.0580 (7)
H3	0.2136	−0.0003	0.6341	0.070*
C4	0.26682 (18)	0.1317 (2)	0.7636 (3)	0.0474 (6)
C5	0.3427 (2)	0.1698 (2)	0.8491 (4)	0.0548 (7)
H5	0.3417	0.2424	0.8987	0.066*
C6	0.4204 (2)	0.0995 (2)	0.8609 (4)	0.0566 (7)
H6	0.4722	0.1243	0.9192	0.068*
C7	0.26414 (17)	0.3597 (2)	0.5642 (3)	0.0468 (6)
C8	0.33831 (18)	0.3209 (2)	0.4704 (4)	0.0532 (7)
H8	0.3359	0.2483	0.4213	0.064*
C9	0.41530 (18)	0.3917 (2)	0.4512 (4)	0.0538 (7)
H9	0.4659	0.3650	0.3914	0.065*
C10	0.41940 (19)	0.5008 (2)	0.5179 (3)	0.0519 (7)
C11	0.34570 (19)	0.5373 (2)	0.6128 (4)	0.0584 (7)
H11	0.3483	0.6103	0.6609	0.070*
C12	0.26858 (19)	0.4679 (2)	0.6375 (3)	0.0551 (7)
H12	0.2198	0.4931	0.7028	0.066*
C13	0.5028 (2)	0.5786 (3)	0.4867 (5)	0.0752 (9)
H13A	0.4860	0.6370	0.4096	0.113*
H13B	0.5537	0.5327	0.4460	0.113*
H13C	0.5215	0.6155	0.5847	0.113*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0420 (3)	0.0668 (4)	0.0582 (4)	0.0045 (3)	−0.0005 (4)	0.0083 (4)
F1	0.1299 (17)	0.0508 (9)	0.1214 (18)	0.0063 (10)	−0.0321 (16)	−0.0197 (11)
O1	0.0640 (15)	0.0999 (18)	0.108 (2)	0.0104 (14)	−0.0161 (15)	0.0259 (17)
O2	0.135 (2)	0.0934 (17)	0.0836 (18)	0.0580 (16)	−0.0025 (17)	−0.0028 (15)
O3	0.0489 (11)	0.0689 (12)	0.0543 (12)	0.0047 (9)	0.0104 (10)	0.0087 (10)
O4	0.0635 (14)	0.0765 (13)	0.0625 (13)	−0.0099 (10)	−0.0104 (11)	−0.0038 (11)
O5	0.0452 (11)	0.0901 (14)	0.1011 (19)	0.0158 (9)	0.0081 (13)	0.0152 (14)
N1	0.0737 (19)	0.0709 (17)	0.0579 (17)	0.0151 (14)	0.0075 (15)	0.0231 (15)
C1	0.0533 (18)	0.0547 (16)	0.0487 (17)	0.0054 (12)	0.0020 (14)	0.0132 (14)
C2	0.078 (2)	0.0415 (14)	0.0605 (19)	−0.0031 (14)	−0.0059 (17)	0.0043 (14)
C3	0.0585 (17)	0.0529 (15)	0.0627 (19)	−0.0129 (13)	−0.0115 (15)	0.0035 (14)
C4	0.0457 (14)	0.0534 (14)	0.0430 (15)	−0.0017 (11)	0.0040 (13)	0.0085 (12)
C5	0.0580 (17)	0.0520 (15)	0.0543 (17)	−0.0027 (13)	−0.0022 (15)	0.0005 (13)
C6	0.0557 (18)	0.0606 (17)	0.0534 (18)	−0.0076 (14)	−0.0060 (15)	0.0069 (14)
C7	0.0431 (13)	0.0520 (13)	0.0453 (17)	0.0104 (10)	0.0012 (13)	0.0046 (13)
C8	0.0524 (16)	0.0467 (13)	0.0604 (17)	0.0088 (12)	0.0042 (15)	−0.0067 (13)
C9	0.0453 (15)	0.0563 (16)	0.0597 (18)	0.0090 (12)	0.0078 (14)	−0.0005 (14)
C10	0.0506 (16)	0.0555 (16)	0.0497 (17)	0.0051 (12)	−0.0056 (13)	0.0021 (12)
C11	0.0692 (18)	0.0491 (13)	0.0568 (18)	0.0042 (12)	−0.0026 (18)	−0.0081 (14)
C12	0.0601 (17)	0.0582 (15)	0.0471 (17)	0.0176 (12)	0.0093 (14)	−0.0015 (13)
C13	0.069 (2)	0.0714 (19)	0.085 (2)	−0.0119 (15)	0.001 (2)	−0.0069 (18)

Geometric parameters (Å, º) top

S1—O3	1.619 (2)	C5—C6	1.374 (4)
S1—O4	1.419 (2)	C6—H6	0.9300
S1—O5	1.4152 (19)	C7—C8	1.390 (4)
S1—C7	1.741 (3)	C7—C12	1.386 (3)
F1—C2	1.332 (3)	C8—H8	0.9300
O1—N1	1.216 (4)	C8—C9	1.375 (3)
O2—N1	1.206 (3)	C9—H9	0.9300
O3—C4	1.401 (3)	C9—C10	1.373 (4)
N1—C1	1.475 (4)	C10—C11	1.382 (4)
C1—C2	1.374 (4)	C10—C13	1.509 (4)
C1—C6	1.380 (4)	C11—H11	0.9300
C2—C3	1.372 (4)	C11—C12	1.374 (4)
C3—H3	0.9300	C12—H12	0.9300
C3—C4	1.371 (4)	C13—H13A	0.9600
C4—C5	1.369 (4)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600

F1—C2—C1	121.8 (3)	C6—C1—N1	117.8 (3)
F1—C2—C3	117.2 (3)	C6—C5—H5	120.4
O1—N1—C1	117.7 (3)	C7—C8—H8	120.5
O2—N1—O1	124.3 (3)	C7—C12—H12	120.3
O2—N1—C1	118.0 (3)	C8—C7—S1	119.45 (19)
O3—S1—C7	103.48 (11)	C8—C9—H9	119.1
O4—S1—O3	107.89 (11)	C9—C8—C7	119.0 (2)
O4—S1—C7	109.59 (13)	C9—C8—H8	120.5
O5—S1—O3	103.14 (14)	C9—C10—C11	118.5 (2)
O5—S1—O4	120.23 (14)	C9—C10—C13	120.2 (3)
O5—S1—C7	110.97 (11)	C10—C9—C8	121.7 (2)
C1—C6—H6	119.9	C10—C9—H9	119.1
C2—C1—N1	122.7 (3)	C10—C11—H11	119.4
C2—C1—C6	119.5 (3)	C10—C13—H13A	109.5
C2—C3—H3	120.7	C10—C13—H13B	109.5
C3—C2—C1	121.0 (3)	C10—C13—H13C	109.5
C3—C4—O3	120.3 (2)	C11—C10—C13	121.3 (3)
C4—O3—S1	117.93 (16)	C11—C12—C7	119.3 (2)
C4—C3—C2	118.6 (3)	C11—C12—H12	120.3
C4—C3—H3	120.7	C12—C7—S1	120.46 (19)
C4—C5—H5	120.4	C12—C7—C8	120.1 (2)
C4—C5—C6	119.1 (3)	C12—C11—C10	121.3 (2)
C5—C4—O3	118.0 (2)	C12—C11—H11	119.4
C5—C4—C3	121.7 (2)	H13A—C13—H13B	109.5
C5—C6—C1	120.2 (3)	H13A—C13—H13C	109.5
C5—C6—H6	119.9	H13B—C13—H13C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.55	3.224 (4)	129

Symmetry code: (i) −x+1, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀FNO₅S
M_r	311.28
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	14.2596 (5), 11.4800 (3), 8.3602 (2)
V (Å³)	1368.57 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)
T_min, T_max	0.979, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	10802, 2251, 1855
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.083, 1.05
No. of reflections	2251
No. of parameters	191
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.23
Absolute structure	Flack (1983), 752 Friedel pairs
Absolute structure parameter	−0.06 (9)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.55	3.224 (4)	129

Symmetry code: (i) −x+1, −y, z+1/2.

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

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