Crystal structure of 1-fluoro-1,3-di­hydro­benzo[c]thio­phene 2,2-dioxide

Zou, Y.; Qiu, Z.; Tang, R.; Yuan, K.; Li, Y.

doi:10.1107/S2056989015016357

organic compounds

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Volume 71| Part 10| October 2015| Page o749

doi:10.1107/S2056989015016357

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Crystal structure of 1-fluoro-1,3-dihydrobenzo[c]thiophene 2,2-dioxide

Ying Zou,^a Zibin Qiu,^a Renming Tang,^a Kaixu Yuan ^a and Ya Li ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, 333 Longteng Road, Shanghai, People's Republic of China
^*Correspondence e-mail: ya.li@sues.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 14 August 2015; accepted 2 September 2015; online 12 September 2015)

In the title compound, C₈H₇FO₂S, the thiophene ring has an envelope conformation, with the S atom bearing the two O atoms being the flap. In the crystal, molecules are linked by C—H⋯O and C—H⋯F interactions, generating a three-dimensional network structure.

Keywords: crystal structure; sulfone; fluorine; dihydrobenzothiophene; C—H⋯O and C—H⋯F interactions.

CCDC reference: 1421889

1. Related literature

For the use of of α-fluoro sulfones in organic synthesis, see: Fukuzumi et al. (2006 ); Li et al. (2006 ); Prakash et al. (2003 ); Zhao et al. (2013 ). For their synthesis, see: Jiang et al. (2014 ); Ni et al. (2008 ).

2. Experimental

2.1. Crystal data

C₈H₇FO₂S
M_r = 186.20
Monoclinic, P 2₁ /c
a = 5.7772 (5) Å
b = 8.3886 (6) Å
c = 16.8717 (12) Å
β = 99.742 (6)°
V = 805.86 (11) Å³
Z = 4
Cu Kα radiation
μ = 3.38 mm⁻¹
T = 296 K
0.05 × 0.03 × 0.02 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.418, T_max = 0.753
6724 measured reflections
1475 independent reflections
1206 reflections with I > 2σ(I)
R_int = 0.080

2.3. Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.205
S = 1.13
1475 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.98 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.95	3.687 (6)	138
C1—H1⋯O1ⁱⁱ	0.98	2.47	3.266 (5)	139
C1—H1⋯O2ⁱⁱ	0.98	3.48	4.331 (6)	147
C4—H4⋯O2ⁱⁱⁱ	0.93	2.54	3.371 (5)	148
C5—H5⋯F1^iv	0.93	2.81	3.640 (5)	150
C8—H8B⋯O2^v	0.97	2.50	3.406 (5)	156
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+2, -z+2; (iii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae, 2006 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 1421889

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015016357/wm5205sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015016357/wm5205Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015016357/wm5205Isup3.pdf

Supporting information file. DOI: 10.1107/S2056989015016357/wm5205Isup4.pdf

Supporting information file. DOI: 10.1107/S2056989015016357/wm5205Isup5.pdf

Supporting information file. DOI: 10.1107/S2056989015016357/wm5205Isup6.cml

checkCIF report

Synthesis and crystallization top

Lithium bis(trimethylsilyl)amide (LiHMDS; 2.2 ml, 1.0 M in THF, 2.2 mmol, 2.2 equiv) and anhydrous ZnCl₂ (341 mg, 2.5 mmol, 2.5 equiv) were dissolved in 12 ml THF. 10 minutes later, 1,3-dihydrobenzo[c]thiophene-2,2-dioxide (168 mg, 1.0 mmol, 1.0 equiv) was added into the mixture under N₂ atmosphere. The reaction was stirred for one hour. Then N-fluorobenzenesulfonimide (NFSI; 2.0 equiv, 632 mg, 2.0 mmol) was added into the mixture in a flash. The reaction was allowed at room temperature for half an hour and quenched by addition of H₂O. After extraction with ethyl acetate, the organic layer was dried over anhydrous Na₂SO₄, filtered and removed under vacuum. The crude product was purified by flash column chromatography on silica gel with ethyl acetate/hexane (1:3) to provide the title compound (97 mg, 52%). The obtained powder was recrystallized from dichloromethane/hexane (1:10) solution to give colourless crystals.

¹H NMR (400 MHz, CDCl₃) δ = 7.64-7.66 (d, J = 8.0 Hz, 1H), 7.56-7.59 (m, 1H), 7.48-7.52 (m, 1H), 7.36-7.38 (d, J = 8.0 Hz, 1H), 6.03 (d, J = 56.4 Hz, 1H), 4.40 (dd, J = 60.0, 16.0 Hz, 2H). ¹⁹F NMR (376 MHz, CDCl₃) δ = -153.70 (d, J = 56.4 Hz). ¹³C NMR (101 MHz, CDCl₃) δ = 128.6 (d, J = 4.0 Hz), 126.1, 125.5 (d, J = 4.0 Hz), 124.8, 122.5, 122.1, 94.2 (d, J = 86.4 Hz), 49.9. MS (EI) m/z: 168 [M + H - 19]⁺. HRMS (EI) m/z: calcd for C₈H₈O₂S [M + H - 19]⁺ 168.0245, found 168.0251.

Refinement top

All H atoms of the phenyl groups were placed at calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The methylene H atoms were found from a difference map. Their positions were refined with C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C).

Results and discussion top

Related literature top

For the use of of α-fluoro sulfones in organic synthesis, see: Fukuzumi et al. (2006); Li et al. (2006); Prakash et al. (2003); Zhao et al. (2013). For their synthesis, see: Jiang et al. (2014); Ni et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae, 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing of the molecules in the unit cell in a view approximately along [010].

1-Fluoro-1,3-dihydrobenzo[c]thiophene 2,2-dioxide top

Crystal data top

C₈H₇FO₂S	F(000) = 384
M_r = 186.20	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 5.7772 (5) Å	Cell parameters from 1262 reflections
b = 8.3886 (6) Å	θ = 5.3–66.3°
c = 16.8717 (12) Å	µ = 3.38 mm⁻¹
β = 99.742 (6)°	T = 296 K
V = 805.86 (11) Å³	Block, colourless
Z = 4	0.05 × 0.03 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	1206 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
φ and ω scans	θ_max = 69.6°, θ_min = 5.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.418, T_max = 0.753	k = −10→9
6724 measured reflections	l = −19→17
1475 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.068	H-atom parameters constrained
wR(F²) = 0.205	w = 1/[σ²(F_o²) + (0.1242P)² + 0.3031P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
1475 reflections	Δρ_max = 0.58 e Å⁻³
109 parameters	Δρ_min = −0.98 e Å⁻³
0 restraints

Crystal data top

C₈H₇FO₂S	V = 805.86 (11) Å³
M_r = 186.20	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 5.7772 (5) Å	µ = 3.38 mm⁻¹
b = 8.3886 (6) Å	T = 296 K
c = 16.8717 (12) Å	0.05 × 0.03 × 0.02 mm
β = 99.742 (6)°

Data collection top

Bruker APEXII CCD diffractometer	1475 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1206 reflections with I > 2σ(I)
T_min = 0.418, T_max = 0.753	R_int = 0.080
6724 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.205	H-atom parameters constrained
S = 1.13	Δρ_max = 0.58 e Å⁻³
1475 reflections	Δρ_min = −0.98 e Å⁻³
109 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.58177 (16)	0.76462 (12)	0.95887 (5)	0.0438 (4)
F1	0.1554 (5)	0.6784 (4)	0.96561 (16)	0.0686 (8)
O1	0.6976 (5)	0.9083 (4)	0.94354 (18)	0.0593 (9)
O2	0.6325 (6)	0.6952 (5)	1.03759 (17)	0.0675 (10)
C1	0.2672 (7)	0.7960 (5)	0.9290 (2)	0.0442 (9)
H1	0.2194	0.9030	0.9431	0.053*
C2	0.2387 (7)	0.7727 (4)	0.8397 (2)	0.0381 (8)
C3	0.0537 (8)	0.8364 (5)	0.7852 (3)	0.0521 (10)
H3	−0.0632	0.8964	0.8027	0.063*
C4	0.0492 (10)	0.8075 (6)	0.7037 (3)	0.0633 (13)
H4	−0.0734	0.8477	0.6661	0.076*
C5	0.2237 (10)	0.7203 (6)	0.6781 (3)	0.0638 (13)
H5	0.2178	0.7029	0.6233	0.077*
C6	0.4093 (8)	0.6576 (5)	0.7325 (2)	0.0512 (10)
H6	0.5276	0.5994	0.7147	0.061*
C7	0.4136 (6)	0.6840 (4)	0.8142 (2)	0.0373 (8)
C8	0.6028 (7)	0.6252 (5)	0.8808 (2)	0.0442 (9)
H8A	0.7564	0.6286	0.8649	0.053*
H8B	0.5711	0.5175	0.8969	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0448 (6)	0.0535 (7)	0.0294 (6)	−0.0075 (4)	−0.0046 (4)	−0.0040 (3)
F1	0.0590 (15)	0.098 (2)	0.0493 (15)	−0.0118 (15)	0.0102 (11)	0.0065 (13)
O1	0.0623 (18)	0.0629 (19)	0.0519 (16)	−0.0229 (15)	0.0075 (13)	−0.0147 (14)
O2	0.068 (2)	0.095 (2)	0.0328 (16)	−0.0078 (18)	−0.0109 (14)	0.0109 (15)
C1	0.047 (2)	0.054 (2)	0.0302 (19)	−0.0005 (17)	0.0026 (14)	−0.0082 (15)
C2	0.045 (2)	0.0384 (19)	0.0283 (18)	−0.0040 (15)	−0.0003 (14)	−0.0037 (13)
C3	0.053 (2)	0.051 (2)	0.047 (2)	0.0017 (18)	−0.0075 (17)	0.0000 (17)
C4	0.078 (3)	0.063 (3)	0.038 (2)	−0.013 (2)	−0.019 (2)	0.0103 (19)
C5	0.092 (4)	0.069 (3)	0.027 (2)	−0.021 (3)	−0.001 (2)	−0.0043 (18)
C6	0.068 (3)	0.052 (2)	0.0358 (19)	−0.0143 (19)	0.0140 (17)	−0.0135 (16)
C7	0.0453 (19)	0.0335 (18)	0.0313 (17)	−0.0072 (14)	0.0011 (14)	−0.0070 (13)
C8	0.0427 (19)	0.043 (2)	0.045 (2)	0.0018 (16)	0.0020 (15)	−0.0037 (16)

Geometric parameters (Å, º) top

S1—O1	1.423 (3)	C3—C4	1.392 (6)
S1—O2	1.434 (3)	C4—H4	0.9300
S1—C1	1.821 (4)	C4—C5	1.373 (8)
S1—C8	1.781 (4)	C5—H5	0.9300
F1—C1	1.381 (5)	C5—C6	1.391 (7)
C1—H1	0.9800	C6—H6	0.9300
C1—C2	1.502 (5)	C6—C7	1.392 (5)
C2—C3	1.393 (5)	C7—C8	1.512 (5)
C2—C7	1.381 (5)	C8—H8A	0.9700
C3—H3	0.9300	C8—H8B	0.9700

O1—S1—O2	118.9 (2)	C3—C4—H4	119.6
O1—S1—C1	107.8 (2)	C5—C4—C3	120.7 (4)
O1—S1—C8	109.19 (19)	C5—C4—H4	119.6
O2—S1—C1	110.6 (2)	C4—C5—H5	119.4
O2—S1—C8	112.9 (2)	C4—C5—C6	121.3 (4)
C8—S1—C1	94.61 (18)	C6—C5—H5	119.4
S1—C1—H1	112.0	C5—C6—H6	120.8
F1—C1—S1	107.1 (3)	C5—C6—C7	118.4 (4)
F1—C1—H1	112.0	C7—C6—H6	120.8
F1—C1—C2	112.1 (3)	C2—C7—C6	120.2 (4)
C2—C1—S1	101.1 (3)	C2—C7—C8	114.8 (3)
C2—C1—H1	112.0	C6—C7—C8	125.0 (4)
C3—C2—C1	123.6 (4)	S1—C8—H8A	111.4
C7—C2—C1	114.9 (3)	S1—C8—H8B	111.4
C7—C2—C3	121.4 (4)	C7—C8—S1	101.8 (2)
C2—C3—H3	121.0	C7—C8—H8A	111.4
C4—C3—C2	118.0 (4)	C7—C8—H8B	111.4
C4—C3—H3	121.0	H8A—C8—H8B	109.3

S1—C1—C2—C3	−156.5 (3)	C1—C2—C7—C8	0.2 (5)
S1—C1—C2—C7	22.5 (4)	C2—C3—C4—C5	−0.7 (7)
F1—C1—C2—C3	89.7 (5)	C2—C7—C8—S1	−23.5 (4)
F1—C1—C2—C7	−91.2 (4)	C3—C2—C7—C6	0.7 (6)
O1—S1—C1—F1	−162.2 (2)	C3—C2—C7—C8	179.3 (4)
O1—S1—C1—C2	80.4 (3)	C3—C4—C5—C6	0.3 (8)
O1—S1—C8—C7	−79.0 (3)	C4—C5—C6—C7	0.6 (7)
O2—S1—C1—F1	−30.6 (3)	C5—C6—C7—C2	−1.0 (6)
O2—S1—C1—C2	−148.1 (3)	C5—C6—C7—C8	−179.6 (4)
O2—S1—C8—C7	146.3 (3)	C6—C7—C8—S1	155.1 (3)
C1—S1—C8—C7	31.6 (3)	C7—C2—C3—C4	0.2 (6)
C1—C2—C3—C4	179.3 (4)	C8—S1—C1—F1	86.0 (3)
C1—C2—C7—C6	−178.4 (3)	C8—S1—C1—C2	−31.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.95	3.687 (6)	138
C1—H1···O1ⁱⁱ	0.98	2.47	3.266 (5)	139
C1—H1···O2ⁱⁱ	0.98	3.48	4.331 (6)	147
C4—H4···O2ⁱⁱⁱ	0.93	2.54	3.371 (5)	148
C5—H5···F1^iv	0.93	2.81	3.640 (5)	150
C8—H8B···O2^v	0.97	2.50	3.406 (5)	156

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+2; (iii) x−1, −y+3/2, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.95	3.687 (6)	137.7
C1—H1···O1ⁱⁱ	0.98	2.47	3.266 (5)	138.5
C1—H1···O2ⁱⁱ	0.98	3.48	4.331 (6)	146.7
C4—H4···O2ⁱⁱⁱ	0.93	2.54	3.371 (5)	148.3
C5—H5···F1^iv	0.93	2.81	3.640 (5)	149.6
C8—H8B···O2^v	0.97	2.50	3.406 (5)	156.3

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+2; (iii) x−1, −y+3/2, z−1/2; (iv) x, −y+3/2, z−1/2; (v) −x+1, −y+1, −z+2.

Acknowledgements

Financial support by the Innovation Program of Shanghai University Students (cx1404008 and cs1404015) is gratefully acknowledged.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Page o749

doi:10.1107/S2056989015016357

Open

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