Crystal structure of 2-ethyl-3-(4-fluoro-phenyl-sulfin-yl)-5,7-dimethyl-1-benzo-furan.

In the title compound, C18H17FO2S, the dihedral angle between the planes of the benzo-furan ring system (r.m.s. deviation = 0.004 Å) and the 4-fluoro-phenyl ring is 86.38 (6)°. The terminal C atom of the ethyl substituent is displaced by 1.444 (3) Å from the benzo-furan ring system to the same side of the mol-ecule as the 4-fluoro-phenyl ring. In the crystal, mol-ecules are linked via pairs of C-H⋯π inter-actions into inversion-related dimers. These dimers are further linked by π-π inter-actions between the benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.715 (3) Å] and between the furan rings of neighbouring mol-ecules [centroid-centroid distance = 3.598 (3) Å]. The mol-ecules are stacked along the a-axis direction. In the sulfinyl group, the S and O atoms are disordered over two sets of sites, with site-occupancy factors of 0.797 (3) and 0.213 (3).

Related literature

For pharmaceutical properties of benzo­furan compounds, see: Aslam et al. (2009 ▶); Galal et al. (2009 ▶); Howlett et al. (1999 ▶); Khan et al. (2005 ▶); Ono et al. (2002 ▶). For natural products with a benzo­furan ring, see: Akgul & Anil (2003 ▶); Soekamto et al. (2003 ▶). For the synthesis of the starting material 2-ethyl-3-(4-fluoro­phenyl­sulfan­yl)-5,7-dimethyl-1-benzo­furan, see: Choi et al. (1999 ▶). For a related structure, see: Choi et al. (2010 ▶).

Experimental

Crystal data

C18H17FO2S

M = 316.38

Triclinic,

a = 9.1523 (2) Å

b = 9.5503 (2) Å

c = 10.3099 (2) Å

α = 65.666 (1)°

β = 81.636 (1)°

γ = 70.782 (1)°

V = 775.29 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 173 K

0.45 × 0.41 × 0.27 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.907, T max = 0.942

14476 measured reflections

3874 independent reflections

3481 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.170

S = 1.08

3874 reflections

209 parameters

17 restraints

H-atom parameters constrained

Δρmax = 0.94 e Å−3

Δρmin = −1.64 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: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814019023/hb7276sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019023/hb7276Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814019023/hb7276Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814019023/hb7276fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. The S1 and O2 atoms of the sulfinyl group are disordered over two positions with site-occupancy factors, from refinement of 0.797 (3) (part A) and 0.213 (3) (part B).

Click here for additional data file.

x y z x y z . DOI: 10.1107/S1600536814019023/hb7276fig2.tif

A view of the C–H⋯π and π–π inter­actions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding and disordered part B atoms were omitted for clarity. [Symmetry codes: (i) −x + 2, −y, −z + 1; (ii) −x + 1, −y, −z + 1.]

CCDC reference: 1020650

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

C18H17FO2S	V = 775.29 (3) Å3
Mr = 316.38	Z = 2
Triclinic, P1	F(000) = 332
Hall symbol: -P 1	Dx = 1.355 Mg m−3
a = 9.1523 (2) Å	Melting point = 379–378 K
b = 9.5503 (2) Å	Mo Kα radiation, λ = 0.71073 Å
c = 10.3099 (2) Å	µ = 0.22 mm−1
α = 65.666 (1)°	T = 173 K
β = 81.636 (1)°	Block, colourless
γ = 70.782 (1)°	0.45 × 0.41 × 0.27 mm

Bruker SMART APEXII CCD diffractometer	3874 independent reflections
Radiation source: rotating anode	3481 reflections with I > 2σ(I)
Graphite multilayer monochromator	Rint = 0.028
Detector resolution: 10.0 pixels mm-1	θmax = 28.5°, θmin = 2.2°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −12→12
Tmin = 0.907, Tmax = 0.942	l = −13→13
14476 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063	Hydrogen site location: difference Fourier map
wR(F2) = 0.170	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0799P)2 + 0.8614P] where P = (Fo2 + 2Fc2)/3
3874 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.94 e Å−3
17 restraints	Δρmin = −1.64 e Å−3

Experimental. 1H NMR (δ p.p.m., CDCl3, 400 Hz): 7.62-7.67 (m, 2H), 7.15-7.21 (m, 2H), 6.85 (s, 2H), 3.13 (q, J =7.52 Hz, 2H), 2.43 (s, 3H), 2.24 (s, 3H), 1.44 (t, J = 7.52 Hz, 3H).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1A	0.46524 (7)	0.39880 (7)	0.27750 (7)	0.0245 (2)	0.797 (3)
O2A	0.3828 (2)	0.4499 (2)	0.39425 (17)	0.0291 (4)	0.797 (3)
S1B	0.47017 (19)	0.40209 (16)	0.3147 (3)	0.0245 (2)	0.20
O2B	0.3618 (7)	0.4565 (9)	0.1973 (6)	0.0291 (4)	0.20
F1	0.9355 (2)	0.7389 (2)	0.05373 (19)	0.0497 (4)
O1	0.69201 (18)	−0.05783 (19)	0.39017 (17)	0.0278 (4)
C1	0.5858 (2)	0.20046 (14)	0.3595 (2)	0.0255 (4)
C2	0.6924 (2)	0.1271 (3)	0.4764 (2)	0.0250 (4)
C3	0.7407 (3)	0.1777 (3)	0.5674 (2)	0.0278 (5)
H3	0.6994	0.2857	0.5605	0.033*
C4	0.8512 (3)	0.0653 (3)	0.6687 (2)	0.0312 (5)
C5	0.9101 (3)	−0.0934 (3)	0.6775 (2)	0.0324 (5)
H5	0.9856	−0.1675	0.7476	0.039*
C6	0.8642 (3)	−0.1485 (3)	0.5895 (2)	0.0286 (5)
C7	0.7543 (2)	−0.0323 (3)	0.4904 (2)	0.0262 (4)
C8	0.5892 (2)	0.0857 (3)	0.3131 (2)	0.0264 (4)
C9	0.9111 (3)	0.1158 (4)	0.7667 (3)	0.0416 (6)
H9A	0.8504	0.2264	0.7538	0.062*
H9B	1.0201	0.1105	0.7439	0.062*
H9C	0.9016	0.0434	0.8657	0.062*
C10	0.9286 (3)	−0.3185 (3)	0.5983 (3)	0.0381 (6)
H10A	0.8436	−0.3642	0.6110	0.057*
H10B	0.9986	−0.3831	0.6794	0.057*
H10C	0.9857	−0.3192	0.5104	0.057*
C11	0.5104 (3)	0.0881 (3)	0.1959 (3)	0.0334 (5)
H11A	0.4131	0.1784	0.1735	0.040*
H11B	0.4830	−0.0132	0.2281	0.040*
C12	0.6102 (3)	0.1066 (3)	0.0612 (3)	0.0388 (6)
H12A	0.6319	0.2102	0.0252	0.058*
H12B	0.5551	0.1027	−0.0113	0.058*
H12C	0.7078	0.0189	0.0832	0.058*
C13	0.61273 (19)	0.4976 (2)	0.2173 (2)	0.0284 (4)
C14	0.6924 (3)	0.4950 (3)	0.0925 (2)	0.0314 (5)
H14	0.6723	0.4362	0.0455	0.038*
C15	0.8004 (3)	0.5770 (3)	0.0365 (3)	0.0334 (5)
H15	0.8551	0.5759	−0.0489	0.040*
C16	0.8272 (3)	0.6608 (3)	0.1073 (3)	0.0333 (5)
C17	0.7502 (3)	0.6671 (3)	0.2305 (3)	0.0352 (5)
H17	0.7718	0.7258	0.2769	0.042*
C18	0.6402 (3)	0.5856 (3)	0.2857 (3)	0.0329 (5)
H18	0.5839	0.5898	0.3698	0.040*

	U11	U22	U33	U12	U13	U23
S1A	0.0258 (3)	0.0285 (3)	0.0181 (4)	−0.0026 (2)	−0.0041 (2)	−0.0109 (2)
O2A	0.0216 (8)	0.0372 (10)	0.0300 (9)	−0.0030 (7)	−0.0004 (5)	−0.0190 (8)
S1B	0.0258 (3)	0.0285 (3)	0.0181 (4)	−0.0026 (2)	−0.0041 (2)	−0.0109 (2)
O2B	0.0216 (8)	0.0372 (10)	0.0300 (9)	−0.0030 (7)	−0.0004 (5)	−0.0190 (8)
F1	0.0540 (10)	0.0477 (9)	0.0512 (10)	−0.0292 (8)	0.0032 (8)	−0.0135 (8)
O1	0.0282 (8)	0.0260 (7)	0.0279 (8)	−0.0071 (6)	−0.0024 (6)	−0.0094 (6)
C1	0.0242 (10)	0.0257 (7)	0.0229 (9)	−0.0056 (6)	−0.0007 (7)	−0.0073 (8)
C2	0.0224 (9)	0.0283 (10)	0.0218 (9)	−0.0083 (8)	0.0016 (7)	−0.0073 (8)
C3	0.0278 (10)	0.0322 (11)	0.0253 (10)	−0.0119 (9)	0.0034 (8)	−0.0118 (9)
C4	0.0280 (11)	0.0438 (13)	0.0237 (10)	−0.0168 (10)	0.0018 (8)	−0.0110 (9)
C5	0.0266 (11)	0.0389 (12)	0.0236 (10)	−0.0112 (9)	−0.0033 (8)	−0.0025 (9)
C6	0.0257 (10)	0.0282 (10)	0.0257 (10)	−0.0087 (8)	0.0010 (8)	−0.0045 (8)
C7	0.0245 (10)	0.0291 (10)	0.0238 (10)	−0.0097 (8)	0.0006 (8)	−0.0083 (8)
C8	0.0240 (10)	0.0291 (10)	0.0240 (10)	−0.0081 (8)	0.0000 (8)	−0.0083 (8)
C9	0.0429 (14)	0.0578 (17)	0.0311 (12)	−0.0218 (13)	−0.0025 (10)	−0.0183 (12)
C10	0.0338 (12)	0.0280 (11)	0.0403 (13)	−0.0046 (9)	−0.0036 (10)	−0.0043 (10)
C11	0.0333 (12)	0.0385 (12)	0.0318 (12)	−0.0107 (10)	−0.0057 (9)	−0.0152 (10)
C12	0.0540 (16)	0.0366 (13)	0.0276 (11)	−0.0157 (11)	−0.0010 (11)	−0.0126 (10)
C13	0.0288 (10)	0.0226 (10)	0.0265 (10)	−0.0019 (7)	−0.0031 (8)	−0.0060 (8)
C14	0.0376 (12)	0.0295 (11)	0.0264 (10)	−0.0074 (9)	−0.0028 (9)	−0.0113 (9)
C15	0.0375 (12)	0.0328 (11)	0.0259 (11)	−0.0084 (10)	0.0011 (9)	−0.0097 (9)
C16	0.0363 (12)	0.0262 (11)	0.0322 (12)	−0.0087 (9)	−0.0043 (9)	−0.0057 (9)
C17	0.0461 (14)	0.0261 (11)	0.0330 (12)	−0.0053 (10)	−0.0081 (10)	−0.0129 (9)
C18	0.0392 (12)	0.0263 (10)	0.0267 (11)	−0.0006 (9)	−0.0011 (9)	−0.0108 (9)

S1A—O2B	1.180 (3)	C8—C11	1.484 (3)
S1A—O2A	1.4943 (9)	C9—H9A	0.9800
S1A—C1	1.7597 (10)	C9—H9B	0.9800
S1A—C13	1.7918 (10)	C9—H9C	0.9800
O2A—S1B	1.182 (2)	C10—H10A	0.9800
S1B—O2B	1.4869 (10)	C10—H10B	0.9800
S1B—C1	1.7633 (10)	C10—H10C	0.9800
S1B—C13	1.7865 (10)	C11—C12	1.527 (4)
F1—C16	1.353 (3)	C11—H11A	0.9900
O1—C8	1.366 (3)	C11—H11B	0.9900
O1—C7	1.387 (3)	C12—H12A	0.9800
C1—C8	1.355 (3)	C12—H12B	0.9800
C1—C2	1.445 (3)	C12—H12C	0.9800
C2—C7	1.391 (3)	C13—C14	1.389 (3)
C2—C3	1.395 (3)	C13—C18	1.395 (3)
C3—C4	1.391 (3)	C14—C15	1.376 (4)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.399 (4)	C15—C16	1.377 (4)
C4—C9	1.513 (3)	C15—H15	0.9500
C5—C6	1.388 (3)	C16—C17	1.374 (4)
C5—H5	0.9500	C17—C18	1.388 (4)
C6—C7	1.384 (3)	C17—H17	0.9500
C6—C10	1.502 (3)	C18—H18	0.9500
O2B—S1A—O2A	98.8 (4)	H9A—C9—H9B	109.5
O2B—S1A—C1	132.7 (4)	C4—C9—H9C	109.5
O2A—S1A—C1	106.79 (11)	H9A—C9—H9C	109.5
O2B—S1A—C13	113.2 (4)	H9B—C9—H9C	109.5
O2A—S1A—C13	104.60 (11)	C6—C10—H10A	109.5
C1—S1A—C13	98.06 (10)	C6—C10—H10B	109.5
S1B—O2A—S1A	11.31 (14)	H10A—C10—H10B	109.5
O2A—S1B—O2B	99.1 (3)	C6—C10—H10C	109.5
O2A—S1B—C1	124.2 (2)	H10A—C10—H10C	109.5
O2B—S1B—C1	112.3 (3)	H10B—C10—H10C	109.5
O2A—S1B—C13	121.5 (2)	C8—C11—C12	112.6 (2)
O2B—S1B—C13	99.4 (3)	C8—C11—H11A	109.1
C1—S1B—C13	98.13 (12)	C12—C11—H11A	109.1
S1A—O2B—S1B	11.63 (11)	C8—C11—H11B	109.1
C8—O1—C7	106.69 (17)	C12—C11—H11B	109.1
C8—C1—C2	108.00 (14)	H11A—C11—H11B	107.8
C8—C1—S1A	120.39 (16)	C11—C12—H12A	109.5
C2—C1—S1A	131.60 (16)	C11—C12—H12B	109.5
C8—C1—S1B	132.68 (19)	H12A—C12—H12B	109.5
C2—C1—S1B	119.05 (19)	C11—C12—H12C	109.5
S1A—C1—S1B	13.29 (10)	H12A—C12—H12C	109.5
C7—C2—C3	119.4 (2)	H12B—C12—H12C	109.5
C7—C2—C1	104.31 (18)	C14—C13—C18	120.08 (16)
C3—C2—C1	136.2 (2)	C14—C13—S1B	130.30 (19)
C4—C3—C2	118.0 (2)	C18—C13—S1B	109.61 (19)
C4—C3—H3	121.0	C14—C13—S1A	117.84 (16)
C2—C3—H3	121.0	C18—C13—S1A	121.90 (17)
C3—C4—C5	120.1 (2)	S1B—C13—S1A	13.08 (10)
C3—C4—C9	119.9 (2)	C15—C14—C13	120.4 (2)
C5—C4—C9	120.0 (2)	C15—C14—H14	119.8
C6—C5—C4	123.6 (2)	C13—C14—H14	119.8
C6—C5—H5	118.2	C14—C15—C16	118.4 (2)
C4—C5—H5	118.2	C14—C15—H15	120.8
C7—C6—C5	114.2 (2)	C16—C15—H15	120.8
C7—C6—C10	122.3 (2)	F1—C16—C17	118.7 (2)
C5—C6—C10	123.5 (2)	F1—C16—C15	118.4 (2)
C6—C7—O1	124.8 (2)	C17—C16—C15	122.9 (2)
C6—C7—C2	124.7 (2)	C16—C17—C18	118.5 (2)
O1—C7—C2	110.49 (18)	C16—C17—H17	120.8
C1—C8—O1	110.49 (18)	C18—C17—H17	120.8
C1—C8—C11	133.2 (2)	C17—C18—C13	119.7 (2)
O1—C8—C11	116.23 (19)	C17—C18—H18	120.2
C4—C9—H9A	109.5	C13—C18—H18	120.2
C4—C9—H9B	109.5
O2B—S1A—O2A—S1B	−169.5 (5)	C10—C6—C7—C2	−179.1 (2)
C1—S1A—O2A—S1B	50.7 (4)	C8—O1—C7—C6	−179.7 (2)
C13—S1A—O2A—S1B	−52.6 (4)	C8—O1—C7—C2	−0.5 (2)
S1A—O2A—S1B—O2B	8.3 (4)	C3—C2—C7—C6	−0.5 (3)
S1A—O2A—S1B—C1	−116.6 (4)	C1—C2—C7—C6	179.3 (2)
S1A—O2A—S1B—C13	115.3 (4)	C3—C2—C7—O1	−179.77 (18)
O2A—S1A—O2B—S1B	8.1 (4)	C1—C2—C7—O1	0.1 (2)
C1—S1A—O2B—S1B	130.9 (7)	C2—C1—C8—O1	−0.7 (2)
C13—S1A—O2B—S1B	−102.0 (5)	S1A—C1—C8—O1	179.05 (14)
O2A—S1B—O2B—S1A	−169.7 (5)	S1B—C1—C8—O1	−174.62 (18)
C1—S1B—O2B—S1A	−36.8 (6)	C2—C1—C8—C11	−178.0 (2)
C13—S1B—O2B—S1A	66.1 (5)	S1A—C1—C8—C11	1.8 (4)
O2B—S1A—C1—C8	13.3 (6)	S1B—C1—C8—C11	8.1 (4)
O2A—S1A—C1—C8	133.10 (19)	C7—O1—C8—C1	0.8 (2)
C13—S1A—C1—C8	−118.93 (19)	C7—O1—C8—C11	178.54 (18)
O2B—S1A—C1—C2	−166.9 (5)	C1—C8—C11—C12	96.1 (3)
O2A—S1A—C1—C2	−47.2 (2)	O1—C8—C11—C12	−81.0 (3)
C13—S1A—C1—C2	60.8 (2)	O2A—S1B—C13—C14	−158.4 (3)
O2B—S1A—C1—S1B	−146.0 (6)	O2B—S1B—C13—C14	−51.6 (4)
O2A—S1A—C1—S1B	−26.3 (2)	C1—S1B—C13—C14	62.8 (3)
C13—S1A—C1—S1B	81.7 (2)	O2A—S1B—C13—C18	21.6 (3)
O2A—S1B—C1—C8	115.2 (3)	O2B—S1B—C13—C18	128.4 (3)
O2B—S1B—C1—C8	−3.8 (4)	C1—S1B—C13—C18	−117.2 (2)
C13—S1B—C1—C8	−107.5 (3)	O2A—S1B—C13—S1A	−139.2 (4)
O2A—S1B—C1—C2	−58.2 (3)	O2B—S1B—C13—S1A	−32.4 (4)
O2B—S1B—C1—C2	−177.2 (4)	C1—S1B—C13—S1A	81.9 (2)
C13—S1B—C1—C2	79.1 (2)	O2B—S1A—C13—C14	−62.9 (4)
O2A—S1B—C1—S1A	139.6 (4)	O2A—S1A—C13—C14	−169.35 (18)
O2B—S1B—C1—S1A	20.6 (4)	C1—S1A—C13—C14	80.87 (19)
C13—S1B—C1—S1A	−83.1 (2)	O2B—S1A—C13—C18	112.2 (4)
C8—C1—C2—C7	0.4 (2)	O2A—S1A—C13—C18	5.7 (2)
S1A—C1—C2—C7	−179.35 (18)	C1—S1A—C13—C18	−104.0 (2)
S1B—C1—C2—C7	175.26 (16)	O2B—S1A—C13—S1B	133.5 (4)
C8—C1—C2—C3	−179.8 (2)	O2A—S1A—C13—S1B	27.1 (2)
S1A—C1—C2—C3	0.4 (4)	C1—S1A—C13—S1B	−82.7 (2)
S1B—C1—C2—C3	−4.9 (4)	C18—C13—C14—C15	0.9 (3)
C7—C2—C3—C4	0.6 (3)	S1B—C13—C14—C15	−179.1 (2)
C1—C2—C3—C4	−179.2 (2)	S1A—C13—C14—C15	176.07 (18)
C2—C3—C4—C5	−0.2 (3)	C13—C14—C15—C16	0.2 (4)
C2—C3—C4—C9	178.0 (2)	C14—C15—C16—F1	178.7 (2)
C3—C4—C5—C6	−0.1 (4)	C14—C15—C16—C17	−0.5 (4)
C9—C4—C5—C6	−178.4 (2)	F1—C16—C17—C18	−179.4 (2)
C4—C5—C6—C7	0.2 (3)	C15—C16—C17—C18	−0.2 (4)
C4—C5—C6—C10	179.5 (2)	C16—C17—C18—C13	1.2 (3)
C5—C6—C7—O1	179.3 (2)	C14—C13—C18—C17	−1.6 (3)
C10—C6—C7—O1	0.0 (3)	S1B—C13—C18—C17	178.40 (19)
C5—C6—C7—C2	0.1 (3)	S1A—C13—C18—C17	−176.58 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···Cg1i	0.98	2.89	3.822 (2)	159

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C13–C18 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯Cg1i	0.98	2.89	3.822 (2)	159

Symmetry code: (i) .