2-(4-Bromo-phen-yl)-5,6-methyl-enedi-oxy-3-phenyl-sulfinyl-1-benzofuran benzene solvate.

In the title compound, C(21)H(13)BrO(4)S·C(6)H(6), the O atom and the phenyl group of the phenyl-sulfinyl substituent are located on opposite sides of the mean plane of the 5,6-methyl-enedioxy-benzofuran fragment; the phenyl ring is almost perpendicular to this plane [83.66 (6)°]. The 4-bromo-phenyl ring is rotated slightly out of the 5,6-methyl-enedioxy-benzo-furan plane, making a dihedral angle of 2.9 (1)°. The crystal structure is stabilized by inter-molecular C-H⋯O hydrogen bonds and inter-molecular C-H⋯π inter-actions. The crystal structure also exhibits π-π inter-actions between the benzene ring and the 4-bromo-phenyl ring of an adjacent mol-ecule [centroid-centroid distance = 3.586 (3) Å].

Related literature

For the crystal structures of similar 5,6-methyl­enedi­oxy-1-benzofuran derivatives, see: Choi et al. (2007 ▶, 2008 ▶). For the pharmacological activity of benzofuran compounds, see: Howlett et al. (1999 ▶); Twyman & Allsop (1999 ▶). For natural products with benzofuran rings, see: Akgul & Anil (2003 ▶); von Reuss & König (2004 ▶).

Experimental

Crystal data

C21H13BrO4S·C6H6

M = 519.39

Monoclinic,

a = 13.8967 (7) Å

b = 12.6640 (7) Å

c = 13.0469 (7) Å

β = 102.418 (1)°

V = 2242.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 1.96 mm−1

T = 173 K

0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.629, T max = 0.679

13417 measured reflections

4886 independent reflections

3946 reflections with I > 2σ(I)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.102

S = 1.02

4886 reflections

298 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.64 e Å−3

Δρmin = −0.65 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037283/kp2232sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037283/kp2232Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H13BrO4S·C6H6	F(000) = 1056
Mr = 519.39	Dx = 1.538 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6564 reflections
a = 13.8967 (7) Å	θ = 2.2–27.5°
b = 12.6640 (7) Å	µ = 1.96 mm−1
c = 13.0469 (7) Å	T = 173 K
β = 102.418 (1)°	Block, colorless
V = 2242.4 (2) Å3	0.40 × 0.20 × 0.20 mm
Z = 4

Bruker SMART CCD diffractometer	4886 independent reflections
Radiation source: fine-focus sealed tube	3946 reflections with I > 2σ(I)
graphite	Rint = 0.075
Detector resolution: 10.0 pixels mm-1	θmax = 27.0°, θmin = 1.5°
φ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −16→8
Tmin = 0.629, Tmax = 0.679	l = −15→16
13417 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)] = 0.036	Hydrogen site location: difference Fourier map
wR(F2) = 0.102	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0572P)2 + 0.3212P] where P = (Fo2 + 2Fc2)/3
4886 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 0.64 e Å−3
6 restraints	Δρmin = −0.65 e Å−3

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
Br	0.201403 (18)	0.26805 (2)	0.115664 (18)	0.03840 (10)
S	0.63758 (4)	0.22232 (4)	0.56951 (4)	0.02291 (13)
O1	0.43951 (10)	0.44110 (11)	0.59753 (11)	0.0246 (3)
O2	0.57823 (12)	0.58271 (13)	0.94388 (13)	0.0359 (4)
O3	0.71273 (11)	0.47027 (13)	0.96114 (12)	0.0311 (3)
O4	0.68316 (11)	0.16954 (12)	0.67099 (11)	0.0302 (3)
C1	0.56264 (14)	0.32535 (16)	0.60145 (15)	0.0224 (4)
C2	0.47437 (14)	0.36076 (16)	0.54372 (16)	0.0226 (4)
C3	0.50610 (14)	0.45414 (16)	0.69083 (16)	0.0230 (4)
C4	0.49371 (15)	0.52551 (17)	0.76854 (17)	0.0267 (4)
H4	0.4400	0.5708	0.7619	0.032*
C5	0.56899 (16)	0.52172 (16)	0.85561 (17)	0.0261 (4)
C6	0.66481 (17)	0.54604 (19)	1.01496 (17)	0.0324 (5)
H6A	0.6472	0.5136	1.0757	0.039*
H6B	0.7088	0.6048	1.0387	0.039*
C7	0.64952 (15)	0.45403 (17)	0.86521 (16)	0.0250 (4)
C8	0.66125 (15)	0.38315 (16)	0.78944 (16)	0.0245 (4)
H8	0.7152	0.3381	0.7972	0.029*
C9	0.58448 (15)	0.38419 (16)	0.69831 (16)	0.0227 (4)
C10	0.41034 (15)	0.33635 (16)	0.44190 (16)	0.0234 (4)
C11	0.32404 (16)	0.39505 (18)	0.40747 (18)	0.0296 (5)
H11	0.3082	0.4482	0.4502	0.036*
C12	0.26182 (16)	0.37585 (19)	0.31148 (18)	0.0319 (5)
H12	0.2051	0.4160	0.2895	0.038*
C13	0.28519 (16)	0.29598 (18)	0.24839 (17)	0.0277 (5)
C14	0.36932 (17)	0.23670 (18)	0.28017 (18)	0.0300 (5)
H14	0.3842	0.1833	0.2372	0.036*
C15	0.43210 (17)	0.25665 (17)	0.37660 (19)	0.0291 (5)
H15	0.4890	0.2166	0.3977	0.035*
C16	0.73086 (15)	0.30455 (17)	0.53476 (16)	0.0243 (4)
C17	0.81941 (17)	0.3206 (2)	0.60380 (19)	0.0423 (6)
H17	0.8325	0.2886	0.6695	0.051*
C18	0.8888 (2)	0.3853 (3)	0.5735 (2)	0.0584 (9)
H18	0.9490	0.3971	0.6193	0.070*
C19	0.8689 (2)	0.4326 (3)	0.4751 (2)	0.0530 (8)
H19	0.9153	0.4772	0.4561	0.064*
C20	0.78115 (18)	0.4138 (2)	0.40579 (19)	0.0381 (6)
H20	0.7688	0.4443	0.3394	0.046*
C21	0.71121 (16)	0.34943 (18)	0.43497 (16)	0.0284 (5)
H21	0.6517	0.3363	0.3884	0.034*
C22	0.0616 (2)	0.5412 (3)	0.1216 (2)	0.0578 (8)
H22	0.1180	0.5166	0.1017	0.069*
C23	−0.0017 (2)	0.4709 (3)	0.1512 (2)	0.0629 (9)
H23	0.0124	0.3991	0.1516	0.076*
C24	−0.0846 (2)	0.5040 (5)	0.1801 (3)	0.0906 (16)
H24	−0.1278	0.4551	0.1987	0.109*
C25	−0.1041 (3)	0.6067 (6)	0.1817 (4)	0.114 (2)
H25	−0.1608	0.6279	0.2028	0.137*
C26	−0.0441 (5)	0.6831 (4)	0.1536 (4)	0.129 (3)
H26	−0.0592	0.7545	0.1557	0.155*
C27	0.0434 (3)	0.6476 (4)	0.1207 (3)	0.0869 (13)
H27	0.0860	0.6955	0.0995	0.104*

	U11	U22	U33	U12	U13	U23
Br	0.04220 (16)	0.04233 (17)	0.02635 (14)	−0.00182 (10)	−0.00222 (10)	−0.00305 (10)
S	0.0252 (3)	0.0199 (3)	0.0232 (3)	0.00213 (19)	0.0043 (2)	−0.0001 (2)
O1	0.0278 (7)	0.0209 (7)	0.0245 (7)	0.0025 (6)	0.0041 (6)	−0.0012 (6)
O2	0.0408 (9)	0.0339 (9)	0.0302 (8)	0.0055 (7)	0.0016 (7)	−0.0113 (7)
O3	0.0329 (8)	0.0324 (8)	0.0263 (8)	0.0004 (7)	0.0024 (6)	−0.0055 (7)
O4	0.0356 (8)	0.0263 (8)	0.0274 (8)	0.0057 (6)	0.0041 (6)	0.0055 (6)
C1	0.0247 (10)	0.0209 (10)	0.0223 (10)	0.0000 (8)	0.0065 (8)	0.0010 (8)
C2	0.0260 (10)	0.0184 (10)	0.0251 (10)	0.0003 (8)	0.0092 (8)	0.0006 (8)
C3	0.0261 (10)	0.0200 (10)	0.0229 (10)	−0.0009 (8)	0.0054 (8)	0.0027 (8)
C4	0.0286 (11)	0.0225 (11)	0.0299 (11)	0.0027 (8)	0.0083 (9)	−0.0001 (9)
C5	0.0338 (11)	0.0195 (10)	0.0263 (11)	−0.0016 (8)	0.0096 (9)	−0.0020 (8)
C6	0.0406 (12)	0.0290 (12)	0.0265 (11)	−0.0005 (10)	0.0047 (9)	−0.0036 (9)
C7	0.0279 (10)	0.0234 (10)	0.0232 (10)	−0.0047 (8)	0.0044 (8)	0.0008 (8)
C8	0.0258 (10)	0.0218 (10)	0.0265 (10)	0.0007 (8)	0.0072 (8)	0.0017 (9)
C9	0.0259 (10)	0.0195 (10)	0.0244 (10)	−0.0005 (8)	0.0090 (8)	0.0007 (8)
C10	0.0270 (10)	0.0199 (10)	0.0238 (10)	−0.0021 (8)	0.0064 (8)	0.0038 (8)
C11	0.0315 (11)	0.0254 (11)	0.0311 (11)	0.0044 (9)	0.0046 (9)	−0.0049 (9)
C12	0.0307 (11)	0.0292 (12)	0.0333 (12)	0.0064 (9)	0.0013 (9)	−0.0007 (10)
C13	0.0314 (11)	0.0269 (11)	0.0228 (10)	−0.0042 (9)	0.0015 (8)	0.0020 (9)
C14	0.0358 (12)	0.0266 (11)	0.0273 (11)	0.0034 (9)	0.0064 (9)	−0.0054 (9)
C15	0.0307 (11)	0.0276 (11)	0.0282 (11)	0.0062 (9)	0.0043 (9)	0.0006 (9)
C16	0.0246 (10)	0.0245 (10)	0.0245 (10)	−0.0007 (8)	0.0065 (8)	−0.0028 (9)
C17	0.0326 (12)	0.0649 (18)	0.0269 (12)	−0.0063 (12)	0.0007 (10)	0.0041 (12)
C18	0.0341 (14)	0.095 (3)	0.0395 (15)	−0.0256 (15)	−0.0062 (12)	0.0027 (16)
C19	0.0452 (15)	0.070 (2)	0.0439 (15)	−0.0286 (14)	0.0111 (12)	0.0008 (15)
C20	0.0414 (13)	0.0430 (15)	0.0304 (12)	−0.0073 (11)	0.0090 (10)	0.0042 (11)
C21	0.0284 (10)	0.0296 (11)	0.0256 (10)	0.0001 (9)	0.0022 (9)	−0.0010 (9)
C22	0.0416 (15)	0.085 (2)	0.0443 (16)	0.0091 (15)	0.0035 (13)	−0.0037 (16)
C23	0.0460 (16)	0.092 (3)	0.0480 (17)	0.0026 (17)	0.0039 (14)	−0.0090 (18)
C24	0.0445 (18)	0.177 (5)	0.0487 (19)	−0.003 (2)	0.0070 (15)	−0.038 (3)
C25	0.072 (3)	0.176 (6)	0.076 (3)	0.057 (3)	−0.025 (2)	−0.081 (4)
C26	0.148 (5)	0.089 (4)	0.102 (4)	0.060 (4)	−0.080 (4)	−0.049 (3)
C27	0.093 (3)	0.076 (3)	0.067 (2)	0.003 (2)	−0.036 (2)	0.000 (2)

Br—C13	1.901 (2)	C12—H12	0.9300
S—O4	1.4968 (15)	C13—C14	1.376 (3)
S—C1	1.774 (2)	C14—C15	1.391 (3)
S—C16	1.795 (2)	C14—H14	0.9300
O1—C3	1.371 (2)	C15—H15	0.9300
O1—C2	1.382 (2)	C16—C17	1.375 (3)
O2—C5	1.370 (3)	C16—C21	1.393 (3)
O2—C6	1.429 (3)	C17—C18	1.387 (4)
O3—C7	1.381 (2)	C17—H17	0.9300
O3—C6	1.435 (3)	C18—C19	1.389 (4)
C1—C2	1.370 (3)	C18—H18	0.9300
C1—C9	1.442 (3)	C19—C20	1.374 (4)
C2—C10	1.464 (3)	C19—H19	0.9300
C3—C9	1.391 (3)	C20—C21	1.383 (3)
C3—C4	1.396 (3)	C20—H20	0.9300
C4—C5	1.370 (3)	C21—H21	0.9300
C4—H4	0.9300	C22—C23	1.365 (5)
C5—C7	1.394 (3)	C22—C27	1.370 (5)
C6—H6A	0.9700	C22—H22	0.9300
C6—H6B	0.9700	C23—C24	1.354 (4)
C7—C8	1.371 (3)	C23—H23	0.9300
C8—C9	1.416 (3)	C24—C25	1.330 (7)
C8—H8	0.9300	C24—H24	0.9300
C10—C15	1.395 (3)	C25—C26	1.377 (8)
C10—C11	1.400 (3)	C25—H25	0.9300
C11—C12	1.382 (3)	C26—C27	1.445 (8)
C11—H11	0.9300	C26—H26	0.9300
C12—C13	1.386 (3)	C27—H27	0.9300
O4—S—C1	106.19 (9)	C14—C13—C12	120.8 (2)
O4—S—C16	106.93 (9)	C14—C13—Br	119.17 (17)
C1—S—C16	97.18 (10)	C12—C13—Br	120.07 (17)
C3—O1—C2	107.24 (15)	C13—C14—C15	120.0 (2)
C5—O2—C6	106.02 (17)	C13—C14—H14	120.0
C7—O3—C6	105.75 (16)	C15—C14—H14	120.0
C2—C1—C9	107.91 (17)	C14—C15—C10	120.5 (2)
C2—C1—S	127.83 (16)	C14—C15—H15	119.8
C9—C1—S	124.22 (15)	C10—C15—H15	119.8
C1—C2—O1	109.40 (17)	C17—C16—C21	121.3 (2)
C1—C2—C10	136.67 (19)	C17—C16—S	120.88 (17)
O1—C2—C10	113.92 (17)	C21—C16—S	117.76 (16)
O1—C3—C9	110.75 (17)	C16—C17—C18	118.7 (2)
O1—C3—C4	123.88 (18)	C16—C17—H17	120.7
C9—C3—C4	125.33 (19)	C18—C17—H17	120.7
C5—C4—C3	112.83 (19)	C17—C18—C19	120.4 (2)
C5—C4—H4	123.6	C17—C18—H18	119.8
C3—C4—H4	123.6	C19—C18—H18	119.8
C4—C5—O2	126.47 (19)	C20—C19—C18	120.3 (2)
C4—C5—C7	123.47 (19)	C20—C19—H19	119.8
O2—C5—C7	110.06 (19)	C18—C19—H19	119.8
O2—C6—O3	108.32 (17)	C19—C20—C21	119.9 (2)
O2—C6—H6A	110.0	C19—C20—H20	120.1
O3—C6—H6A	110.0	C21—C20—H20	120.1
O2—C6—H6B	110.0	C20—C21—C16	119.3 (2)
O3—C6—H6B	110.0	C20—C21—H21	120.3
H6A—C6—H6B	108.4	C16—C21—H21	120.3
C8—C7—O3	126.87 (19)	C23—C22—C27	121.0 (4)
C8—C7—C5	123.75 (19)	C23—C22—H22	119.5
O3—C7—C5	109.38 (18)	C27—C22—H22	119.5
C7—C8—C9	114.48 (18)	C24—C23—C22	121.0 (4)
C7—C8—H8	122.8	C24—C23—H23	119.5
C9—C8—H8	122.8	C22—C23—H23	119.5
C3—C9—C8	120.13 (18)	C25—C24—C23	119.7 (5)
C3—C9—C1	104.69 (17)	C25—C24—H24	120.2
C8—C9—C1	135.18 (19)	C23—C24—H24	120.2
C15—C10—C11	118.1 (2)	C24—C25—C26	123.1 (4)
C15—C10—C2	122.52 (19)	C24—C25—H25	118.4
C11—C10—C2	119.36 (18)	C26—C25—H25	118.4
C12—C11—C10	121.5 (2)	C25—C26—C27	117.2 (4)
C12—C11—H11	119.2	C25—C26—H26	121.4
C10—C11—H11	119.2	C27—C26—H26	121.4
C11—C12—C13	119.1 (2)	C22—C27—C26	118.0 (5)
C11—C12—H12	120.5	C22—C27—H27	121.0
C13—C12—H12	120.5	C26—C27—H27	121.0
O4—S—C1—C2	−144.86 (18)	S—C1—C9—C3	−178.71 (15)
C16—S—C1—C2	105.13 (19)	C2—C1—C9—C8	178.1 (2)
O4—S—C1—C9	32.39 (19)	S—C1—C9—C8	0.4 (3)
C16—S—C1—C9	−77.62 (18)	C1—C2—C10—C15	1.9 (4)
C9—C1—C2—O1	1.4 (2)	O1—C2—C10—C15	−179.02 (18)
S—C1—C2—O1	179.01 (14)	C1—C2—C10—C11	−177.7 (2)
C9—C1—C2—C10	−179.5 (2)	O1—C2—C10—C11	1.4 (3)
S—C1—C2—C10	−1.9 (4)	C15—C10—C11—C12	−0.4 (3)
C3—O1—C2—C1	−1.2 (2)	C2—C10—C11—C12	179.2 (2)
C3—O1—C2—C10	179.43 (16)	C10—C11—C12—C13	0.6 (3)
C2—O1—C3—C9	0.6 (2)	C11—C12—C13—C14	−0.3 (3)
C2—O1—C3—C4	−177.09 (19)	C11—C12—C13—Br	−179.72 (17)
O1—C3—C4—C5	178.27 (18)	C12—C13—C14—C15	0.0 (3)
C9—C3—C4—C5	0.9 (3)	Br—C13—C14—C15	179.35 (17)
C3—C4—C5—O2	179.17 (19)	C13—C14—C15—C10	0.2 (3)
C3—C4—C5—C7	0.2 (3)	C11—C10—C15—C14	0.0 (3)
C6—O2—C5—C4	176.6 (2)	C2—C10—C15—C14	−179.6 (2)
C6—O2—C5—C7	−4.3 (2)	O4—S—C16—C17	−8.5 (2)
C5—O2—C6—O3	6.8 (2)	C1—S—C16—C17	100.9 (2)
C7—O3—C6—O2	−6.7 (2)	O4—S—C16—C21	170.16 (16)
C6—O3—C7—C8	−175.7 (2)	C1—S—C16—C21	−80.45 (18)
C6—O3—C7—C5	4.1 (2)	C21—C16—C17—C18	1.8 (4)
C4—C5—C7—C8	−1.0 (3)	S—C16—C17—C18	−179.6 (2)
O2—C5—C7—C8	179.93 (19)	C16—C17—C18—C19	−0.2 (5)
C4—C5—C7—O3	179.20 (19)	C17—C18—C19—C20	−1.5 (5)
O2—C5—C7—O3	0.1 (2)	C18—C19—C20—C21	1.5 (5)
O3—C7—C8—C9	−179.72 (18)	C19—C20—C21—C16	0.1 (4)
C5—C7—C8—C9	0.5 (3)	C17—C16—C21—C20	−1.8 (3)
O1—C3—C9—C8	−179.05 (17)	S—C16—C21—C20	179.57 (18)
C4—C3—C9—C8	−1.4 (3)	C27—C22—C23—C24	0.4 (5)
O1—C3—C9—C1	0.2 (2)	C22—C23—C24—C25	−1.3 (5)
C4—C3—C9—C1	177.88 (19)	C23—C24—C25—C26	1.0 (7)
C7—C8—C9—C3	0.6 (3)	C24—C25—C26—C27	0.3 (7)
C7—C8—C9—C1	−178.4 (2)	C23—C22—C27—C26	0.9 (5)
C2—C1—C9—C3	−1.0 (2)	C25—C26—C27—C22	−1.2 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4i	0.93	2.43	3.290 (3)	154
C14—H14···Cg1ii	0.93	2.72	3.531 (3)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O4i	0.93	2.43	3.290 (3)	154
C14—H14⋯Cg1ii	0.93	2.72	3.531 (3)	147

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C1/C2/O1/C3/C9 furan ring.