organic compounds
c]thiophene 2,2-dioxide
of 1-fluoro-1,3-dihydrobenzo[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
In the title compound, C8H7FO2S, the thiophene ring has an 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 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
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S2056989015016357/wm5205sup1.cif
contains datablock I. DOI: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
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
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.
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 Uiso(H) = 1.2Ueq(C). The methylene H atoms were found from a difference map. Their positions were refined with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2009); cell
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).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]. |
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 |
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 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 |
C8H7FO2S | V = 805.86 (11) Å3 |
Mr = 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)° |
Bruker APEXII CCD diffractometer | 1475 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1206 reflections with I > 2σ(I) |
Tmin = 0.418, Tmax = 0.753 | Rint = 0.080 |
6724 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.58 e Å−3 |
1475 reflections | Δρmin = −0.98 e Å−3 |
109 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. |
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* |
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) |
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) |
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. |
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···F1iv | 0.93 | 2.81 | 3.640 (5) | 149.6 |
C8—H8B···O2v | 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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