Crystal structure of 5-bromo-2,4,6-trimethyl-3-[(2-methyl-phen-yl)sulfin-yl]-1-benzo-furan.

In the title compound, C18H17BrO2S, the dihedral angle between the mean planes of the benzo-furan [r.m.s. deviation = 0.025 (2) Å] and the 2-methyl-benzene rings is 87.87 (5)°. In the crystal, mol-ecules are linked into supra-molecular layers parallel to (0-11) by C-H⋯O hydrogen bonds and Br⋯Br [3.4521 (5) Å] contacts. These are connected into a three-dimensional architecture via C-H⋯π inter-actions, which link inversion-related mol-ecules into dimers, and π-π inter-actions between the benzene and furan rings [centroid-centroid distance = 3.573 (2) Å].

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 a related structure, see: Choi et al. (2014 ▸). For synthetic details, see: Choi et al. (1999 ▸).

Experimental

Crystal data

C18H17BrO2S

M = 377.29

Triclinic,

a = 7.4011 (2) Å

b = 10.6609 (2) Å

c = 11.1857 (2) Å

α = 67.265 (1)°

β = 86.593 (1)°

γ = 79.384 (1)°

V = 800.00 (3) Å3

Z = 2

Mo Kα radiation

μ = 2.70 mm−1

T = 173 K

0.60 × 0.54 × 0.48 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.269, T max = 0.746

14745 measured reflections

3982 independent reflections

3297 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.087

S = 1.05

3982 reflections

204 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.79 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: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg,1998 ▸); software used to prepare material for publication: SHELXL2014.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015013687/tk5377sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013687/tk5377Isup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015013687/tk5377Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015013687/tk5377fig1.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 . DOI: 10.1107/S2056989015013687/tk5377fig2.tif

A view of the C—H⋯O and Br⋯Br 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; (iv) − x, − y + 2, − z + 1; (v) x − 1, y, z.]

Click here for additional data file.

x y z x y z . DOI: 10.1107/S2056989015013687/tk5377fig3.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 were omitted for clarity. [Symmetry codes: (ii) − x + 1, − y + 2, − z; (iii) − x + 1, − y + 1, − z + 1.]

CCDC reference: 1413623

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

C18H17BrO2S	Z = 2
Mr = 377.29	F(000) = 384
Triclinic, P1	Dx = 1.566 Mg m−3
a = 7.4011 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6609 (2) Å	Cell parameters from 7576 reflections
c = 11.1857 (2) Å	θ = 2.8–28.3°
α = 67.265 (1)°	µ = 2.70 mm−1
β = 86.593 (1)°	T = 173 K
γ = 79.384 (1)°	Block, colourless
V = 800.00 (3) Å3	0.60 × 0.54 × 0.48 mm

Bruker SMART APEXII CCD diffractometer	3982 independent reflections
Radiation source: rotating anode	3297 reflections with I > 2σ(I)
Detector resolution: 10.0 pixels mm-1	Rint = 0.046
φ and ω scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.269, Tmax = 0.746	k = −14→14
14745 measured reflections	l = −14→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.087	w = 1/[σ2(Fo2) + (0.0371P)2 + 0.3816P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3982 reflections	Δρmax = 0.48 e Å−3
204 parameters	Δρmin = −0.79 e Å−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick 2014, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (2)

Experimental. 1H NMR (δ p.p.m., CDCl3, 400 Hz): 8.01 (d, J = 7.52 Hz, 1H), 7.35-7.44 (m, 2H), 7.15-7.23 (m, 2H), 2.64 (s, 3H), 2.53 (s, 3H), 2.50 (s, 3H), 2.15 (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.

	x	y	z	Uiso*/Ueq
Br1	0.18479 (4)	0.88031 (3)	0.48841 (3)	0.04996 (12)
S1	0.47494 (6)	0.56515 (5)	0.10695 (5)	0.02289 (12)
O1	0.82901 (18)	0.52534 (15)	0.36828 (13)	0.0255 (3)
O2	0.29324 (19)	0.52076 (15)	0.14556 (15)	0.0318 (3)
C1	0.5830 (2)	0.5705 (2)	0.24007 (18)	0.0215 (4)
C2	0.5307 (2)	0.63609 (19)	0.33233 (18)	0.0212 (4)
C3	0.3713 (3)	0.7126 (2)	0.36069 (19)	0.0252 (4)
C4	0.3916 (3)	0.7625 (2)	0.4560 (2)	0.0305 (5)
C5	0.5531 (3)	0.7344 (2)	0.5293 (2)	0.0320 (5)
C6	0.7045 (3)	0.6511 (2)	0.5047 (2)	0.0292 (4)
H6	0.8151	0.6258	0.5538	0.035*
C7	0.6896 (3)	0.6060 (2)	0.40654 (18)	0.0232 (4)
C8	0.7605 (3)	0.5054 (2)	0.26755 (19)	0.0230 (4)
C9	0.1912 (3)	0.7347 (2)	0.2948 (2)	0.0353 (5)
H9A	0.0923	0.7254	0.3583	0.053*
H9B	0.1951	0.6658	0.2564	0.053*
H9C	0.1682	0.8275	0.2265	0.053*
C10	0.5626 (4)	0.7902 (3)	0.6331 (2)	0.0456 (6)
H10A	0.6826	0.7532	0.6771	0.068*
H10B	0.4653	0.7624	0.6961	0.068*
H10C	0.5460	0.8912	0.5936	0.068*
C11	0.8919 (3)	0.4230 (2)	0.2093 (2)	0.0315 (5)
H11A	0.8326	0.4174	0.1360	0.047*
H11B	0.9303	0.3298	0.2745	0.047*
H11C	0.9999	0.4674	0.1790	0.047*
C12	0.4240 (3)	0.7459 (2)	0.00352 (18)	0.0237 (4)
C13	0.2409 (3)	0.8030 (2)	−0.0253 (2)	0.0354 (5)
H13	0.1482	0.7498	0.0148	0.042*
C14	0.1930 (3)	0.9375 (3)	−0.1124 (3)	0.0458 (6)
H14	0.0671	0.9775	−0.1315	0.055*
C15	0.3276 (4)	1.0137 (3)	−0.1718 (2)	0.0425 (6)
H15	0.2950	1.1065	−0.2312	0.051*
C16	0.5101 (3)	0.9544 (2)	−0.1444 (2)	0.0356 (5)
H16	0.6019	1.0078	−0.1858	0.043*
C17	0.5636 (3)	0.8195 (2)	−0.05849 (19)	0.0266 (4)
C18	0.7640 (3)	0.7562 (3)	−0.0369 (2)	0.0373 (5)
H18A	0.8362	0.8142	−0.1052	0.056*
H18B	0.7826	0.6637	−0.0391	0.056*
H18C	0.8037	0.7494	0.0478	0.056*

	U11	U22	U33	U12	U13	U23
Br1	0.05418 (19)	0.03685 (17)	0.05438 (19)	0.00746 (11)	0.01541 (12)	−0.02160 (13)
S1	0.0205 (2)	0.0245 (3)	0.0253 (2)	−0.00667 (18)	−0.00178 (17)	−0.0098 (2)
O1	0.0211 (7)	0.0289 (8)	0.0257 (7)	−0.0014 (5)	−0.0027 (5)	−0.0104 (6)
O2	0.0237 (7)	0.0313 (8)	0.0385 (8)	−0.0127 (6)	−0.0026 (6)	−0.0074 (7)
C1	0.0181 (8)	0.0234 (10)	0.0229 (9)	−0.0051 (7)	0.0006 (7)	−0.0081 (8)
C2	0.0211 (9)	0.0195 (9)	0.0206 (9)	−0.0045 (7)	0.0020 (7)	−0.0047 (7)
C3	0.0254 (9)	0.0205 (10)	0.0240 (10)	−0.0038 (7)	0.0041 (7)	−0.0028 (8)
C4	0.0375 (11)	0.0194 (10)	0.0291 (11)	−0.0006 (8)	0.0082 (8)	−0.0062 (8)
C5	0.0500 (13)	0.0205 (10)	0.0221 (10)	−0.0050 (9)	0.0016 (9)	−0.0051 (8)
C6	0.0370 (11)	0.0247 (11)	0.0234 (10)	−0.0047 (8)	−0.0046 (8)	−0.0059 (8)
C7	0.0245 (9)	0.0200 (10)	0.0220 (9)	−0.0033 (7)	0.0003 (7)	−0.0047 (8)
C8	0.0208 (9)	0.0244 (10)	0.0241 (10)	−0.0058 (7)	0.0003 (7)	−0.0089 (8)
C9	0.0229 (10)	0.0347 (12)	0.0435 (13)	0.0015 (8)	0.0022 (9)	−0.0128 (10)
C10	0.0743 (18)	0.0328 (13)	0.0322 (13)	−0.0039 (12)	−0.0018 (12)	−0.0173 (11)
C11	0.0218 (9)	0.0345 (12)	0.0386 (12)	0.0011 (8)	0.0011 (8)	−0.0172 (10)
C12	0.0271 (9)	0.0242 (10)	0.0205 (9)	−0.0055 (8)	−0.0020 (7)	−0.0086 (8)
C13	0.0252 (10)	0.0353 (12)	0.0372 (12)	−0.0051 (9)	−0.0058 (9)	−0.0040 (10)
C14	0.0367 (13)	0.0393 (14)	0.0466 (15)	0.0009 (10)	−0.0116 (11)	−0.0022 (11)
C15	0.0552 (15)	0.0263 (12)	0.0369 (13)	−0.0047 (11)	−0.0060 (11)	−0.0022 (10)
C16	0.0467 (13)	0.0309 (12)	0.0300 (11)	−0.0169 (10)	0.0021 (9)	−0.0082 (9)
C17	0.0299 (10)	0.0317 (11)	0.0232 (10)	−0.0108 (8)	0.0013 (8)	−0.0136 (9)
C18	0.0287 (11)	0.0438 (14)	0.0376 (12)	−0.0146 (10)	0.0073 (9)	−0.0110 (10)

Br1—C4	1.905 (2)	C9—H9C	0.9800
Br1—Br1i	3.4521 (5)	C10—H10A	0.9800
S1—O2	1.4921 (14)	C10—H10B	0.9800
S1—C1	1.7561 (19)	C10—H10C	0.9800
S1—C12	1.805 (2)	C11—H11A	0.9800
O1—C8	1.366 (2)	C11—H11B	0.9800
O1—C7	1.376 (2)	C11—H11C	0.9800
C1—C8	1.360 (3)	C12—C13	1.381 (3)
C1—C2	1.454 (3)	C12—C17	1.399 (3)
C2—C7	1.395 (3)	C13—C14	1.381 (3)
C2—C3	1.399 (3)	C13—H13	0.9500
C3—C4	1.389 (3)	C14—C15	1.377 (4)
C3—C9	1.498 (3)	C14—H14	0.9500
C4—C5	1.409 (3)	C15—C16	1.379 (4)
C5—C6	1.381 (3)	C15—H15	0.9500
C5—C10	1.505 (3)	C16—C17	1.384 (3)
C6—C7	1.375 (3)	C16—H16	0.9500
C6—H6	0.9500	C17—C18	1.504 (3)
C8—C11	1.481 (3)	C18—H18A	0.9800
C9—H9A	0.9800	C18—H18B	0.9800
C9—H9B	0.9800	C18—H18C	0.9800
C4—Br1—Br1i	173.50 (6)	C5—C10—H10B	109.5
O2—S1—C1	110.19 (9)	H10A—C10—H10B	109.5
O2—S1—C12	105.80 (9)	C5—C10—H10C	109.5
C1—S1—C12	101.64 (9)	H10A—C10—H10C	109.5
C8—O1—C7	106.53 (14)	H10B—C10—H10C	109.5
C8—C1—C2	106.98 (16)	C8—C11—H11A	109.5
C8—C1—S1	117.93 (15)	C8—C11—H11B	109.5
C2—C1—S1	135.02 (15)	H11A—C11—H11B	109.5
C7—C2—C3	119.21 (18)	C8—C11—H11C	109.5
C7—C2—C1	104.32 (16)	H11A—C11—H11C	109.5
C3—C2—C1	136.46 (18)	H11B—C11—H11C	109.5
C4—C3—C2	115.32 (18)	C13—C12—C17	121.35 (19)
C4—C3—C9	122.90 (19)	C13—C12—S1	116.73 (15)
C2—C3—C9	121.76 (19)	C17—C12—S1	121.36 (15)
C3—C4—C5	125.3 (2)	C14—C13—C12	119.8 (2)
C3—C4—Br1	117.17 (16)	C14—C13—H13	120.1
C5—C4—Br1	117.52 (16)	C12—C13—H13	120.1
C6—C5—C4	117.8 (2)	C15—C14—C13	120.0 (2)
C6—C5—C10	120.1 (2)	C15—C14—H14	120.0
C4—C5—C10	122.0 (2)	C13—C14—H14	120.0
C7—C6—C5	117.64 (19)	C14—C15—C16	119.6 (2)
C7—C6—H6	121.2	C14—C15—H15	120.2
C5—C6—H6	121.2	C16—C15—H15	120.2
C6—C7—O1	124.63 (17)	C15—C16—C17	122.1 (2)
C6—C7—C2	124.46 (19)	C15—C16—H16	119.0
O1—C7—C2	110.91 (16)	C17—C16—H16	119.0
C1—C8—O1	111.23 (17)	C16—C17—C12	117.10 (19)
C1—C8—C11	133.54 (19)	C16—C17—C18	120.40 (19)
O1—C8—C11	115.20 (16)	C12—C17—C18	122.48 (19)
C3—C9—H9A	109.5	C17—C18—H18A	109.5
C3—C9—H9B	109.5	C17—C18—H18B	109.5
H9A—C9—H9B	109.5	H18A—C18—H18B	109.5
C3—C9—H9C	109.5	C17—C18—H18C	109.5
H9A—C9—H9C	109.5	H18A—C18—H18C	109.5
H9B—C9—H9C	109.5	H18B—C18—H18C	109.5
C5—C10—H10A	109.5
O2—S1—C1—C8	130.07 (16)	C3—C2—C7—C6	−2.7 (3)
C12—S1—C1—C8	−118.10 (16)	C1—C2—C7—C6	178.32 (19)
O2—S1—C1—C2	−53.3 (2)	C3—C2—C7—O1	177.36 (16)
C12—S1—C1—C2	58.6 (2)	C1—C2—C7—O1	−1.6 (2)
C8—C1—C2—C7	1.7 (2)	C2—C1—C8—O1	−1.1 (2)
S1—C1—C2—C7	−175.25 (16)	S1—C1—C8—O1	176.39 (13)
C8—C1—C2—C3	−177.1 (2)	C2—C1—C8—C11	−179.1 (2)
S1—C1—C2—C3	6.0 (4)	S1—C1—C8—C11	−1.6 (3)
C7—C2—C3—C4	5.3 (3)	C7—O1—C8—C1	0.1 (2)
C1—C2—C3—C4	−176.1 (2)	C7—O1—C8—C11	178.51 (17)
C7—C2—C3—C9	−173.01 (18)	O2—S1—C12—C13	−3.79 (19)
C1—C2—C3—C9	5.6 (3)	C1—S1—C12—C13	−118.91 (17)
C2—C3—C4—C5	−4.3 (3)	O2—S1—C12—C17	−175.31 (16)
C9—C3—C4—C5	174.0 (2)	C1—S1—C12—C17	69.58 (17)
C2—C3—C4—Br1	174.84 (13)	C17—C12—C13—C14	−3.1 (3)
C9—C3—C4—Br1	−6.9 (3)	S1—C12—C13—C14	−174.6 (2)
C3—C4—C5—C6	0.3 (3)	C12—C13—C14—C15	1.0 (4)
Br1—C4—C5—C6	−178.87 (15)	C13—C14—C15—C16	0.5 (4)
C3—C4—C5—C10	−178.6 (2)	C14—C15—C16—C17	0.0 (4)
Br1—C4—C5—C10	2.2 (3)	C15—C16—C17—C12	−2.0 (3)
C4—C5—C6—C7	2.7 (3)	C15—C16—C17—C18	176.6 (2)
C10—C5—C6—C7	−178.4 (2)	C13—C12—C17—C16	3.5 (3)
C5—C6—C7—O1	178.41 (18)	S1—C12—C17—C16	174.66 (16)
C5—C6—C7—C2	−1.5 (3)	C13—C12—C17—C18	−175.1 (2)
C8—O1—C7—C6	−178.95 (19)	S1—C12—C17—C18	−3.9 (3)
C8—O1—C7—C2	1.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2	0.98	2.33	3.274 (3)	162
C11—H11C···O2ii	0.98	2.32	3.276 (2)	166
C15—H15···Cg1iii	0.95	2.88	3.659 (3)	140

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the C2C7 benzene ring.

DHA	DH	HA	D A	DHA
C9H9BO2	0.98	2.33	3.274(3)	162
C11H11CO2i	0.98	2.32	3.276(2)	166
C15H15Cg1ii	0.95	2.88	3.659(3)	140

Symmetry codes: (i) ; (ii) .