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

Abstract

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.

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 ▸).

Experimental  

Crystal data  

• C₈H₇FO₂S

• M _r = 186.20

• Monoclinic,

• a = 5.7772 (5) Å

• b = 8.3886 (6) Å

• c = 16.8717 (12) Å

• β = 99.742 (6)°

• V = 805.86 (11) ų

• Z = 4

• Cu Kα radiation

• μ = 3.38 mm⁻¹

• T = 296 K

• 0.05 × 0.03 × 0.02 mm

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

Refinement  

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 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

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.

Supplementary Material

CCDC reference: 1421889

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C3H3O1i	0.93	2.95	3.687(6)	138
C1H1O1ii	0.98	2.47	3.266(5)	139
C1H1O2ii	0.98	3.48	4.331(6)	147
C4H4O2iii	0.93	2.54	3.371(5)	148
C5H5F1iv	0.93	2.81	3.640(5)	150
C8H8BO2v	0.97	2.50	3.406(5)	156

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

S1. Synthesis and crystallization

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.

S2. Refinement

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).

Figures

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].

Crystal data

C8H7FO2S	F(000) = 384
Mr = 186.20	Dx = 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

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

Refinement

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(Fo2) + (0.1242P)2 + 0.3031P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
1475 reflections	Δρmax = 0.58 e Å−3
109 parameters	Δρmin = −0.98 e Å−3
0 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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···F1iv	0.93	2.81	3.640 (5)	150
C8—H8B···O2v	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.