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

In the title compound, C18H17ClO2S, the dihedral angle between the planes of the benzo-furan ring [r.m.s. deviation = 0.013 (1) Å] and the 4-methyl-phenyl ring is 87.37 (5)°. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and π-π inter-actions between the furan and benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.525 (2) Å]. In addition, an S⋯S [3.6584 (9) Å] contact is observed.

Related literature

For the pharmacological properties of benzo­furan compounds, see: Aslam et al. (2009 ▶); Galal et al. (2009 ▶); Howlett et al. (1999 ▶); Wahab 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-2,4,6-trimethyl-3-(4-methyl­phenyl­sulfan­yl)-1-benzo­furan, see: Choi et al. (1999 ▶). For a related structure, see: Choi et al. (2012 ▶).

Experimental

Crystal data

C18H17ClO2S

M = 332.83

Triclinic,

a = 8.7938 (2) Å

b = 9.1775 (3) Å

c = 10.7298 (3) Å

α = 86.571 (1)°

β = 69.157 (1)°

γ = 81.093 (2)°

V = 799.51 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.37 mm−1

T = 173 K

0.60 × 0.56 × 0.08 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.807, T max = 0.971

14763 measured reflections

3988 independent reflections

3502 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.124

S = 1.05

3988 reflections

203 parameters

H-atom parameters constrained

Δρmax = 0.83 e Å−3

Δρmin = −0.41 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/S160053681402385X/nk2227sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681402385X/nk2227Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681402385X/nk2227Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681402385X/nk2227fig1.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 z x y z x y z x y z x y z x y z . DOI: 10.1107/S160053681402385X/nk2227fig2.tif

A view of the C—H⋯O, π–π and S⋯S 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 + 1, y, z; (ii) − x + 1, − y + 2, − z + 1; (iii) − x + 1, − y + 1, − z + 1; (iv) − x, − y + 2, − z + 1; (v) x − 1, y, z; (vi) x, y − 1, z.]

CCDC reference: 1031568

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

C18H17ClO2S	Z = 2
Mr = 332.83	F(000) = 348
Triclinic, P1	Dx = 1.383 Mg m−3
Hall symbol: -P 1	Melting point = 467–466 K
a = 8.7938 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1775 (3) Å	Cell parameters from 6565 reflections
c = 10.7298 (3) Å	θ = 2.6–28.3°
α = 86.571 (1)°	µ = 0.37 mm−1
β = 69.157 (1)°	T = 173 K
γ = 81.093 (2)°	Block, colourless
V = 799.51 (4) Å3	0.60 × 0.56 × 0.08 mm

Bruker SMART APEXII CCD diffractometer	3988 independent reflections
Radiation source: rotating anode	3502 reflections with I > 2σ(I)
Graphite multilayer monochromator	Rint = 0.048
Detector resolution: 10.0 pixels mm-1	θmax = 28.4°, θmin = 2.0°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −12→12
Tmin = 0.807, Tmax = 0.971	l = −11→14
14763 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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F2) = 0.124	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.2785P] where P = (Fo2 + 2Fc2)/3
3988 reflections	(Δ/σ)max < 0.001
203 parameters	Δρmax = 0.83 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Experimental. 1H NMR (δ p.p.m., CDCl3, 400 Hz): 7.34 (d, J = 8.24 Hz, 2H), 7.22 (d, J = 7.84 Hz, 2H), 7.19 (s, 1H), 2.71 (s, 3H), 2.43 (s, 3H), 2.37 (s, 3H), 2.32 (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	0.73398 (7)	0.38071 (5)	0.09920 (5)	0.04987 (16)
S1	0.14021 (5)	0.82594 (5)	0.46437 (4)	0.03532 (13)
O1	0.54038 (13)	0.77389 (12)	0.54951 (11)	0.0305 (2)
O2	0.06142 (17)	0.69774 (17)	0.45239 (15)	0.0502 (4)
C1	0.33771 (18)	0.76626 (16)	0.46945 (16)	0.0281 (3)
C2	0.47994 (18)	0.66515 (15)	0.39027 (15)	0.0256 (3)
C3	0.5174 (2)	0.56896 (16)	0.28374 (16)	0.0298 (3)
C4	0.6780 (2)	0.49579 (17)	0.23736 (16)	0.0321 (3)
C5	0.7994 (2)	0.50928 (18)	0.29109 (17)	0.0330 (3)
C6	0.75771 (19)	0.60170 (17)	0.39906 (16)	0.0315 (3)
H6	0.8345	0.6131	0.4403	0.038*
C7	0.60010 (19)	0.67636 (16)	0.44414 (15)	0.0265 (3)
C8	0.38130 (19)	0.82609 (17)	0.56227 (16)	0.0296 (3)
C9	0.3921 (3)	0.5445 (2)	0.2249 (2)	0.0471 (5)
H9A	0.4114	0.5990	0.1406	0.071*
H9B	0.2817	0.5794	0.2872	0.071*
H9C	0.4015	0.4390	0.2084	0.071*
C10	0.9703 (2)	0.4263 (2)	0.2351 (2)	0.0486 (5)
H10A	1.0322	0.4416	0.2921	0.073*
H10B	1.0256	0.4623	0.1449	0.073*
H10C	0.9645	0.3209	0.2320	0.073*
C11	0.2955 (2)	0.9357 (2)	0.66964 (18)	0.0405 (4)
H11A	0.3379	1.0297	0.6427	0.061*
H11B	0.3145	0.9000	0.7515	0.061*
H11C	0.1773	0.9499	0.6857	0.061*
C12	0.19683 (19)	0.91671 (17)	0.30487 (16)	0.0303 (3)
C13	0.1421 (2)	0.87745 (19)	0.20800 (19)	0.0374 (4)
H13	0.0840	0.7954	0.2211	0.045*
C14	0.1729 (2)	0.9595 (2)	0.09110 (19)	0.0426 (4)
H14	0.1359	0.9324	0.0238	0.051*
C15	0.2563 (3)	1.07992 (19)	0.07025 (18)	0.0433 (4)
C16	0.3090 (3)	1.11627 (19)	0.1702 (2)	0.0448 (4)
H16	0.3671	1.1982	0.1576	0.054*
C17	0.2795 (2)	1.03701 (19)	0.28696 (19)	0.0383 (4)
H17	0.3155	1.0645	0.3547	0.046*
C18	0.2873 (4)	1.1712 (2)	−0.0548 (2)	0.0668 (7)
H18A	0.4004	1.1425	−0.1153	0.100*
H18B	0.2711	1.2758	−0.0323	0.100*
H18C	0.2105	1.1550	−0.0983	0.100*

	U11	U22	U33	U12	U13	U23
Cl1	0.0693 (3)	0.0399 (2)	0.0368 (2)	0.0026 (2)	−0.0170 (2)	−0.01002 (18)
S1	0.0252 (2)	0.0470 (3)	0.0337 (2)	−0.00534 (16)	−0.01096 (16)	0.00375 (17)
O1	0.0335 (6)	0.0326 (5)	0.0308 (6)	−0.0075 (4)	−0.0165 (5)	−0.0015 (4)
O2	0.0404 (7)	0.0647 (9)	0.0563 (9)	−0.0267 (6)	−0.0252 (7)	0.0181 (7)
C1	0.0271 (7)	0.0302 (7)	0.0285 (7)	−0.0066 (6)	−0.0109 (6)	0.0033 (6)
C2	0.0271 (7)	0.0255 (6)	0.0278 (7)	−0.0082 (5)	−0.0129 (6)	0.0045 (5)
C3	0.0373 (8)	0.0276 (7)	0.0295 (8)	−0.0077 (6)	−0.0168 (7)	0.0012 (6)
C4	0.0420 (9)	0.0266 (7)	0.0274 (7)	−0.0058 (6)	−0.0116 (7)	0.0016 (6)
C5	0.0314 (8)	0.0323 (8)	0.0312 (8)	−0.0045 (6)	−0.0072 (6)	0.0067 (6)
C6	0.0292 (7)	0.0346 (8)	0.0342 (8)	−0.0089 (6)	−0.0146 (6)	0.0059 (6)
C7	0.0298 (7)	0.0264 (7)	0.0265 (7)	−0.0085 (5)	−0.0123 (6)	0.0024 (5)
C8	0.0309 (7)	0.0297 (7)	0.0293 (8)	−0.0062 (6)	−0.0117 (6)	0.0031 (6)
C9	0.0541 (11)	0.0450 (10)	0.0563 (12)	−0.0038 (8)	−0.0359 (10)	−0.0133 (9)
C10	0.0346 (9)	0.0530 (11)	0.0465 (11)	0.0025 (8)	−0.0043 (8)	0.0032 (9)
C11	0.0484 (10)	0.0385 (9)	0.0327 (9)	−0.0041 (7)	−0.0122 (8)	−0.0044 (7)
C12	0.0262 (7)	0.0323 (7)	0.0310 (8)	0.0008 (6)	−0.0103 (6)	0.0003 (6)
C13	0.0385 (9)	0.0350 (8)	0.0419 (9)	−0.0027 (7)	−0.0190 (8)	−0.0017 (7)
C14	0.0548 (11)	0.0390 (9)	0.0354 (9)	0.0051 (8)	−0.0216 (8)	−0.0067 (7)
C15	0.0565 (11)	0.0307 (8)	0.0335 (9)	0.0074 (7)	−0.0097 (8)	−0.0024 (7)
C16	0.0544 (11)	0.0300 (8)	0.0477 (11)	−0.0071 (8)	−0.0149 (9)	0.0007 (7)
C17	0.0429 (9)	0.0356 (8)	0.0399 (9)	−0.0045 (7)	−0.0190 (8)	−0.0032 (7)
C18	0.105 (2)	0.0425 (11)	0.0395 (11)	0.0014 (12)	−0.0150 (12)	0.0042 (9)

Cl1—C4	1.7500 (16)	C9—H9C	0.9800
S1—O2	1.4882 (14)	C10—H10A	0.9800
S1—C1	1.7574 (15)	C10—H10B	0.9800
S1—C12	1.7950 (17)	C10—H10C	0.9800
S1—S1i	3.6584 (9)	C11—H11A	0.9800
O1—C8	1.3672 (19)	C11—H11B	0.9800
O1—C7	1.3813 (18)	C11—H11C	0.9800
C1—C8	1.357 (2)	C12—C13	1.377 (2)
C1—C2	1.458 (2)	C12—C17	1.381 (2)
C2—C7	1.392 (2)	C13—C14	1.386 (3)
C2—C3	1.399 (2)	C13—H13	0.9500
C3—C4	1.393 (2)	C14—C15	1.384 (3)
C3—C9	1.501 (2)	C14—H14	0.9500
C4—C5	1.405 (2)	C15—C16	1.386 (3)
C5—C6	1.384 (2)	C15—C18	1.501 (3)
C5—C10	1.502 (2)	C16—C17	1.372 (3)
C6—C7	1.376 (2)	C16—H16	0.9500
C6—H6	0.9500	C17—H17	0.9500
C8—C11	1.481 (2)	C18—H18A	0.9800
C9—H9A	0.9800	C18—H18B	0.9800
C9—H9B	0.9800	C18—H18C	0.9800
O2—S1—C1	110.50 (8)	C5—C10—H10A	109.5
O2—S1—C12	106.80 (8)	C5—C10—H10B	109.5
C1—S1—C12	98.98 (7)	H10A—C10—H10B	109.5
O2—S1—S1i	113.79 (6)	C5—C10—H10C	109.5
C1—S1—S1i	134.58 (5)	H10A—C10—H10C	109.5
C12—S1—S1i	77.68 (5)	H10B—C10—H10C	109.5
C8—O1—C7	106.51 (11)	C8—C11—H11A	109.5
C8—C1—C2	107.06 (13)	C8—C11—H11B	109.5
C8—C1—S1	118.18 (12)	H11A—C11—H11B	109.5
C2—C1—S1	134.71 (12)	C8—C11—H11C	109.5
C7—C2—C3	118.93 (14)	H11A—C11—H11C	109.5
C7—C2—C1	104.37 (13)	H11B—C11—H11C	109.5
C3—C2—C1	136.70 (14)	C13—C12—C17	120.71 (16)
C4—C3—C2	115.52 (14)	C13—C12—S1	120.19 (13)
C4—C3—C9	122.27 (15)	C17—C12—S1	118.68 (13)
C2—C3—C9	122.20 (15)	C12—C13—C14	119.00 (17)
C3—C4—C5	125.18 (15)	C12—C13—H13	120.5
C3—C4—Cl1	117.32 (12)	C14—C13—H13	120.5
C5—C4—Cl1	117.49 (13)	C15—C14—C13	121.47 (17)
C6—C5—C4	118.13 (15)	C15—C14—H14	119.3
C6—C5—C10	119.95 (16)	C13—C14—H14	119.3
C4—C5—C10	121.92 (17)	C14—C15—C16	117.83 (17)
C7—C6—C5	117.09 (14)	C14—C15—C18	121.9 (2)
C7—C6—H6	121.5	C16—C15—C18	120.3 (2)
C5—C6—H6	121.5	C17—C16—C15	121.75 (18)
C6—C7—O1	124.07 (13)	C17—C16—H16	119.1
C6—C7—C2	125.10 (14)	C15—C16—H16	119.1
O1—C7—C2	110.83 (13)	C16—C17—C12	119.23 (16)
C1—C8—O1	111.21 (13)	C16—C17—H17	120.4
C1—C8—C11	133.88 (15)	C12—C17—H17	120.4
O1—C8—C11	114.89 (14)	C15—C18—H18A	109.5
C3—C9—H9A	109.5	C15—C18—H18B	109.5
C3—C9—H9B	109.5	H18A—C18—H18B	109.5
H9A—C9—H9B	109.5	C15—C18—H18C	109.5
C3—C9—H9C	109.5	H18A—C18—H18C	109.5
H9A—C9—H9C	109.5	H18B—C18—H18C	109.5
H9B—C9—H9C	109.5
O2—S1—C1—C8	−134.63 (14)	C8—O1—C7—C2	−0.45 (16)
C12—S1—C1—C8	113.57 (14)	C3—C2—C7—C6	1.5 (2)
S1i—S1—C1—C8	32.06 (17)	C1—C2—C7—C6	−178.85 (15)
O2—S1—C1—C2	48.36 (18)	C3—C2—C7—O1	−178.86 (13)
C12—S1—C1—C2	−63.44 (17)	C1—C2—C7—O1	0.82 (16)
S1i—S1—C1—C2	−144.96 (13)	C2—C1—C8—O1	0.66 (18)
C8—C1—C2—C7	−0.88 (17)	S1—C1—C8—O1	−177.12 (10)
S1—C1—C2—C7	176.36 (13)	C2—C1—C8—C11	179.10 (17)
C8—C1—C2—C3	178.70 (17)	S1—C1—C8—C11	1.3 (3)
S1—C1—C2—C3	−4.1 (3)	C7—O1—C8—C1	−0.16 (17)
C7—C2—C3—C4	−2.4 (2)	C7—O1—C8—C11	−178.91 (13)
C1—C2—C3—C4	178.08 (16)	O2—S1—C12—C13	10.13 (16)
C7—C2—C3—C9	176.67 (16)	C1—S1—C12—C13	124.85 (14)
C1—C2—C3—C9	−2.9 (3)	S1i—S1—C12—C13	−101.30 (13)
C2—C3—C4—C5	1.6 (2)	O2—S1—C12—C17	−177.26 (13)
C9—C3—C4—C5	−177.46 (17)	C1—S1—C12—C17	−62.55 (14)
C2—C3—C4—Cl1	−177.10 (11)	S1i—S1—C12—C17	71.31 (13)
C9—C3—C4—Cl1	3.8 (2)	C17—C12—C13—C14	0.8 (2)
C3—C4—C5—C6	0.3 (3)	S1—C12—C13—C14	173.25 (13)
Cl1—C4—C5—C6	179.01 (12)	C12—C13—C14—C15	−0.4 (3)
C3—C4—C5—C10	179.99 (16)	C13—C14—C15—C16	0.2 (3)
Cl1—C4—C5—C10	−1.3 (2)	C13—C14—C15—C18	−178.73 (18)
C4—C5—C6—C7	−1.3 (2)	C14—C15—C16—C17	−0.4 (3)
C10—C5—C6—C7	178.96 (15)	C18—C15—C16—C17	178.56 (19)
C5—C6—C7—O1	−179.13 (14)	C15—C16—C17—C12	0.8 (3)
C5—C6—C7—C2	0.5 (2)	C13—C12—C17—C16	−1.0 (3)
C8—O1—C7—C6	179.22 (15)	S1—C12—C17—C16	−173.55 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ii	0.95	2.30	3.180 (2)	154
C17—H17···O1iii	0.95	2.56	3.434 (2)	153

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C6H6O2i	0.95	2.30	3.180(2)	154
C17H17O1ii	0.95	2.56	3.434(2)	153

Symmetry codes: (i) ; (ii) .