Crystal structure of 5-chloro-3-(4-fluoro-phenyl-sulfin-yl)-2,4,6-trimethyl-1-benzo-furan.

In the title compound, C17H14ClFO2S, the dihedral angle between the mean planes of the benzo-furan ring system [maximum deviation = 0.037 (2) Å] and the 4-fluoro-benzene ring is 71.92 (5)°. An intra-molecular C-H⋯O hydrogen bond occurs. In the crystal, mol-ecules are linked by π-π stacking between the benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.7103 (10) Å]. These mol-ecules are further linked by C-S⋯π [S⋯centroid = 3.570 (1) Å] and C-H⋯O inter-actions, resulting in a three-dimensional supra-molecular network.

Related literature

For the pharmacological 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 5-chloro-3-(4-fluoro­phenyl­sulfan­yl)-2,4,6-trimethyl-1-benzo­furan, see: Choi et al. (1999 ▶). For a related structure, see: Choi et al. (2012 ▶).

Experimental

Crystal data

C17H14ClFO2S

M = 336.79

Monoclinic,

a = 21.7503 (3) Å

b = 10.6444 (2) Å

c = 16.4061 (3) Å

β = 126.622 (1)°

V = 3048.49 (9) Å3

Z = 8

Mo Kα radiation

μ = 0.40 mm−1

T = 173 K

0.43 × 0.26 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.846, T max = 0.908

14427 measured reflections

3777 independent reflections

3158 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.096

S = 1.06

3777 reflections

202 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.38 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) global, I. DOI: 10.1107/S1600536814019229/xu5819sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019229/xu5819Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814019229/xu5819Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814019229/xu5819fig1.tif

The mol­ecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.

Click here for additional data file.

x y x y x y y . DOI: 10.1107/S1600536814019229/xu5819fig2.tif

A view of the C—H⋯O, C—S⋯π and π⋯π inter­actions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry codes: (i) − x + , y − , − z + 3/2; (ii) − x + 1, − y + 1, − z + 1; (iii) 1.5 − x + , y + , − y + .]

CCDC reference: 1021158

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

C17H14ClFO2S	F(000) = 1392
Mr = 336.79	Dx = 1.468 Mg m−3
Monoclinic, C2/c	Melting point = 433–432 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.7503 (3) Å	Cell parameters from 6565 reflections
b = 10.6444 (2) Å	θ = 2.6–28.3°
c = 16.4061 (3) Å	µ = 0.40 mm−1
β = 126.622 (1)°	T = 173 K
V = 3048.49 (9) Å3	Block, colourless
Z = 8	0.43 × 0.26 × 0.25 mm

Bruker SMART APEXII CCD diffractometer	3777 independent reflections
Radiation source: rotating anode	3158 reflections with I > 2σ(I)
Graphite multilayer monochromator	Rint = 0.030
Detector resolution: 10.0 pixels mm-1	θmax = 28.3°, θmin = 2.2°
φ and ω scans	h = −28→28
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −14→13
Tmin = 0.846, Tmax = 0.908	l = −17→21
14427 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)] = 0.037	Hydrogen site location: difference Fourier map
wR(F2) = 0.096	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0482P)2 + 1.6356P] where P = (Fo2 + 2Fc2)/3
3777 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Experimental. 1H NMR (δ p.p.m., CDCl3, 400 Hz): 7.42-7.49 (m, 2H), 7.21 (s, 1H), 7.11-7.17 (m, 2H), 2.72 (s, 3H), 2.44 (s, 3H), 2.31 (s, 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
Cl1	0.53070 (2)	0.33359 (4)	0.37985 (3)	0.03606 (13)
S1	0.74572 (2)	0.73246 (4)	0.72173 (3)	0.02365 (11)
F1	0.93275 (7)	0.44638 (11)	0.63815 (9)	0.0507 (3)
O1	0.64319 (6)	0.49502 (10)	0.78458 (8)	0.0269 (2)
O2	0.70024 (6)	0.82105 (10)	0.63429 (8)	0.0292 (3)
C1	0.68686 (8)	0.61394 (14)	0.71580 (11)	0.0226 (3)
C2	0.63706 (8)	0.51802 (14)	0.64153 (11)	0.0213 (3)
C3	0.61055 (8)	0.48595 (14)	0.54264 (11)	0.0221 (3)
C4	0.56460 (8)	0.37943 (14)	0.50245 (11)	0.0241 (3)
C5	0.54266 (8)	0.30586 (15)	0.55238 (12)	0.0265 (3)
C6	0.56660 (8)	0.34393 (15)	0.64791 (12)	0.0266 (3)
H6	0.5515	0.2996	0.6836	0.032*
C7	0.61300 (8)	0.44806 (14)	0.68942 (11)	0.0232 (3)
C8	0.68791 (9)	0.59471 (15)	0.79844 (11)	0.0262 (3)
C9	0.63008 (9)	0.56232 (16)	0.48421 (11)	0.0283 (3)
H9A	0.6735	0.5237	0.4901	0.042*
H9B	0.6438	0.6478	0.5118	0.042*
H9C	0.5857	0.5654	0.4126	0.042*
C10	0.49526 (10)	0.18871 (17)	0.50524 (15)	0.0374 (4)
H10A	0.4903	0.1467	0.5542	0.056*
H10B	0.5203	0.1320	0.4862	0.056*
H10C	0.4443	0.2111	0.4445	0.056*
C11	0.72805 (11)	0.65747 (18)	0.89850 (13)	0.0383 (4)
H11A	0.6906	0.6839	0.9099	0.057*
H11B	0.7556	0.7312	0.8998	0.057*
H11C	0.7646	0.5988	0.9521	0.057*
C12	0.80080 (8)	0.63903 (14)	0.69532 (11)	0.0225 (3)
C13	0.83516 (9)	0.52796 (15)	0.74711 (12)	0.0284 (3)
H13	0.8277	0.4970	0.7949	0.034*
C14	0.88046 (10)	0.46287 (16)	0.72827 (13)	0.0331 (4)
H14	0.9048	0.3866	0.7629	0.040*
C15	0.88957 (10)	0.51084 (16)	0.65836 (13)	0.0327 (4)
C16	0.85635 (9)	0.62098 (16)	0.60663 (12)	0.0299 (4)
H16	0.8635	0.6511	0.5583	0.036*
C17	0.81203 (9)	0.68691 (14)	0.62708 (11)	0.0255 (3)
H17	0.7895	0.7648	0.5942	0.031*

	U11	U22	U33	U12	U13	U23
Cl1	0.0410 (2)	0.0357 (3)	0.0314 (2)	−0.00531 (17)	0.0216 (2)	−0.01340 (17)
S1	0.0279 (2)	0.0221 (2)	0.0255 (2)	−0.00352 (14)	0.01845 (17)	−0.00428 (14)
F1	0.0588 (7)	0.0477 (7)	0.0658 (8)	0.0197 (6)	0.0481 (7)	0.0053 (6)
O1	0.0290 (6)	0.0332 (6)	0.0228 (5)	−0.0028 (5)	0.0177 (5)	0.0011 (4)
O2	0.0361 (6)	0.0221 (6)	0.0356 (6)	0.0038 (5)	0.0247 (5)	0.0023 (5)
C1	0.0241 (7)	0.0236 (8)	0.0232 (7)	−0.0011 (6)	0.0158 (6)	−0.0016 (6)
C2	0.0220 (7)	0.0216 (7)	0.0220 (7)	0.0020 (6)	0.0140 (6)	0.0010 (6)
C3	0.0233 (7)	0.0228 (7)	0.0234 (7)	0.0034 (6)	0.0156 (6)	−0.0003 (6)
C4	0.0235 (7)	0.0235 (8)	0.0238 (7)	0.0035 (6)	0.0133 (6)	−0.0032 (6)
C5	0.0205 (7)	0.0224 (8)	0.0329 (8)	0.0016 (6)	0.0139 (7)	0.0004 (6)
C6	0.0229 (7)	0.0268 (8)	0.0309 (8)	0.0027 (6)	0.0165 (7)	0.0072 (6)
C7	0.0221 (7)	0.0253 (8)	0.0229 (7)	0.0030 (6)	0.0138 (6)	0.0019 (6)
C8	0.0268 (8)	0.0301 (8)	0.0242 (7)	−0.0009 (6)	0.0166 (7)	−0.0006 (6)
C9	0.0332 (8)	0.0314 (9)	0.0252 (8)	−0.0028 (7)	0.0202 (7)	−0.0030 (6)
C10	0.0341 (9)	0.0292 (9)	0.0456 (10)	−0.0074 (7)	0.0220 (8)	−0.0049 (8)
C11	0.0463 (10)	0.0478 (11)	0.0248 (8)	−0.0100 (8)	0.0234 (8)	−0.0070 (7)
C12	0.0221 (7)	0.0221 (7)	0.0233 (7)	−0.0024 (6)	0.0136 (6)	−0.0026 (6)
C13	0.0301 (8)	0.0269 (8)	0.0295 (8)	−0.0008 (6)	0.0185 (7)	0.0035 (6)
C14	0.0339 (9)	0.0256 (8)	0.0384 (9)	0.0065 (7)	0.0209 (8)	0.0071 (7)
C15	0.0331 (9)	0.0316 (9)	0.0404 (9)	0.0038 (7)	0.0256 (8)	−0.0032 (7)
C16	0.0355 (9)	0.0308 (9)	0.0324 (8)	−0.0001 (7)	0.0251 (8)	0.0014 (7)
C17	0.0294 (8)	0.0223 (8)	0.0270 (8)	0.0000 (6)	0.0181 (7)	0.0012 (6)

Cl1—C4	1.7487 (15)	C9—H9A	0.9800
S1—O2	1.4943 (11)	C9—H9B	0.9800
S1—C1	1.7581 (16)	C9—H9C	0.9800
S1—C12	1.7977 (15)	C10—H10A	0.9800
F1—C15	1.3543 (19)	C10—H10B	0.9800
O1—C8	1.3637 (19)	C10—H10C	0.9800
O1—C7	1.3767 (18)	C11—H11A	0.9800
C1—C8	1.358 (2)	C11—H11B	0.9800
C1—C2	1.458 (2)	C11—H11C	0.9800
C2—C7	1.391 (2)	C12—C17	1.378 (2)
C2—C3	1.402 (2)	C12—C13	1.386 (2)
C3—C4	1.390 (2)	C13—C14	1.382 (2)
C3—C9	1.499 (2)	C13—H13	0.9500
C4—C5	1.406 (2)	C14—C15	1.374 (2)
C5—C6	1.385 (2)	C14—H14	0.9500
C5—C10	1.505 (2)	C15—C16	1.373 (2)
C6—C7	1.375 (2)	C16—C17	1.386 (2)
C6—H6	0.9500	C16—H16	0.9500
C8—C11	1.481 (2)	C17—H17	0.9500
O2—S1—C1	110.89 (7)	H9A—C9—H9C	109.5
O2—S1—C12	105.80 (7)	H9B—C9—H9C	109.5
C1—S1—C12	99.07 (7)	C5—C10—H10A	109.5
C8—O1—C7	106.37 (11)	C5—C10—H10B	109.5
C8—C1—C2	106.89 (13)	H10A—C10—H10B	109.5
C8—C1—S1	118.35 (12)	C5—C10—H10C	109.5
C2—C1—S1	134.60 (11)	H10A—C10—H10C	109.5
C7—C2—C3	119.32 (14)	H10B—C10—H10C	109.5
C7—C2—C1	104.18 (12)	C8—C11—H11A	109.5
C3—C2—C1	136.49 (14)	C8—C11—H11B	109.5
C4—C3—C2	115.50 (13)	H11A—C11—H11B	109.5
C4—C3—C9	122.47 (13)	C8—C11—H11C	109.5
C2—C3—C9	122.03 (13)	H11A—C11—H11C	109.5
C3—C4—C5	125.13 (14)	H11B—C11—H11C	109.5
C3—C4—Cl1	117.63 (12)	C17—C12—C13	121.44 (15)
C5—C4—Cl1	117.24 (12)	C17—C12—S1	117.25 (12)
C6—C5—C4	117.84 (14)	C13—C12—S1	121.15 (12)
C6—C5—C10	120.25 (15)	C14—C13—C12	119.09 (15)
C4—C5—C10	121.90 (15)	C14—C13—H13	120.5
C7—C6—C5	117.75 (14)	C12—C13—H13	120.5
C7—C6—H6	121.1	C15—C14—C13	118.54 (15)
C5—C6—H6	121.1	C15—C14—H14	120.7
C6—C7—O1	124.54 (14)	C13—C14—H14	120.7
C6—C7—C2	124.32 (14)	F1—C15—C16	117.87 (16)
O1—C7—C2	111.12 (13)	F1—C15—C14	118.86 (15)
C1—C8—O1	111.43 (13)	C16—C15—C14	123.27 (15)
C1—C8—C11	133.34 (15)	C15—C16—C17	117.94 (15)
O1—C8—C11	115.22 (13)	C15—C16—H16	121.0
C3—C9—H9A	109.5	C17—C16—H16	121.0
C3—C9—H9B	109.5	C12—C17—C16	119.69 (15)
H9A—C9—H9B	109.5	C12—C17—H17	120.2
C3—C9—H9C	109.5	C16—C17—H17	120.2
O2—S1—C1—C8	−126.73 (13)	C8—O1—C7—C2	−0.91 (16)
C12—S1—C1—C8	122.41 (13)	C3—C2—C7—C6	3.0 (2)
O2—S1—C1—C2	58.56 (17)	C1—C2—C7—C6	−177.73 (14)
C12—S1—C1—C2	−52.31 (16)	C3—C2—C7—O1	−178.47 (13)
C8—C1—C2—C7	−0.45 (17)	C1—C2—C7—O1	0.84 (16)
S1—C1—C2—C7	174.69 (13)	C2—C1—C8—O1	−0.09 (18)
C8—C1—C2—C3	178.67 (17)	S1—C1—C8—O1	−176.16 (10)
S1—C1—C2—C3	−6.2 (3)	C2—C1—C8—C11	178.60 (18)
C7—C2—C3—C4	−3.6 (2)	S1—C1—C8—C11	2.5 (3)
C1—C2—C3—C4	177.39 (16)	C7—O1—C8—C1	0.60 (17)
C7—C2—C3—C9	175.93 (14)	C7—O1—C8—C11	−178.34 (14)
C1—C2—C3—C9	−3.1 (3)	O2—S1—C12—C17	20.45 (14)
C2—C3—C4—C5	1.2 (2)	C1—S1—C12—C17	135.32 (13)
C9—C3—C4—C5	−178.27 (14)	O2—S1—C12—C13	−164.15 (12)
C2—C3—C4—Cl1	−179.26 (11)	C1—S1—C12—C13	−49.28 (14)
C9—C3—C4—Cl1	1.2 (2)	C17—C12—C13—C14	−1.2 (2)
C3—C4—C5—C6	2.0 (2)	S1—C12—C13—C14	−176.44 (12)
Cl1—C4—C5—C6	−177.49 (11)	C12—C13—C14—C15	−0.2 (2)
C3—C4—C5—C10	−177.52 (15)	C13—C14—C15—F1	−178.81 (16)
Cl1—C4—C5—C10	3.0 (2)	C13—C14—C15—C16	0.5 (3)
C4—C5—C6—C7	−2.8 (2)	F1—C15—C16—C17	179.87 (15)
C10—C5—C6—C7	176.77 (15)	C14—C15—C16—C17	0.5 (3)
C5—C6—C7—O1	−177.99 (14)	C13—C12—C17—C16	2.3 (2)
C5—C6—C7—C2	0.4 (2)	S1—C12—C17—C16	177.70 (12)
C8—O1—C7—C6	177.66 (14)	C15—C16—C17—C12	−1.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2	0.98	2.45	3.3901 (19)	161
C13—H13···O2i	0.95	2.46	3.3191 (19)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O2	0.98	2.45	3.3901 (19)	161
C13—H13⋯O2i	0.95	2.46	3.3191 (19)	150

Symmetry code: (i) .