1,3-Bis(4-methoxy­phen­yl)-2-benzothio­phene

Palani, K.; Amaladass, P.; Mohanakrishnan, A.K.; Ponnuswamy, M.N.

doi:10.1107/S1600536805039589

1,3-Bis(4-methoxyphenyl)-2-benzothiophene

K. Palani, P. Amaladass, A. K. Mohanakrishnan and M. N. Ponnuswamy

In the title compound, C₂₂H₁₈O₂S, the two benzene rings are twisted away from the thiophene ring by 34.99 (9) and 41.57 (9)°. C—H

O and C—H

π hydrogen bonds are observed in the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039589/ci6716sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039589/ci6716Isup2.hkl Contains datablock I

CCDC reference: 268130

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.058
wR factor = 0.235
Data-to-parameter ratio = 22.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT128_ALERT_4_C Non-standard setting of Space group Pbca    ....    Pcab
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Most Schiff bases and their thiophene derivatives possess pharmacological activities such as antibacterial, anticancer, anti-inflammatory and antitoxic properties (Gewald et al., 1996 or 1966). The diaryl-substituted heterocyclic molecules act as selective COX-2 inhibitors (Portevin et al., 2000) and antitumor agents (Szczepankiewicz et al., 2001 or 2000). In view of this importance, the crystal structure of the title compound, (I), has been determined and the results are presented here.

A ZORTEP (Zsolnai, 1997) plot of the molecule is shown in Fig.1. The bond lengths and bond angles (Table 1) in the thiophene moiety are comparable to those reported for 4-{5-[3,4-dimethyl-5-(3,4,5-trimethoxyphenyl)thiophen-2-yl]-2-methoxyphenyl}morpholine (Shi et al., 2004). The C9–C14 and C16–C21 benzene rings are oriented at angles of 34.99 (9) and 41.57 (9)°, respectively, with respect to the thiophene ring. The dihedral angle between the C9–C14 and C16–C21 benzene rings is 71.2 (1)°. Both the methoxy groups are coplanar with the attached rings. The crystal packing is stabilized by C—H···O and C—H···π type hydrogen bonds (Table 2 and Fig. 2). In Table 2, Cg1 and Cg2 denote the centroids of the C16—C21 and C9—C14 benzene rings, respectively.

Experimental top

4-Methoxymagnesium bromide was prepared from 4-bromoanisole (23 mmol) and Mg (25 mmol). 4-Methoxymagnesium bromide was added to a solution of pthalide (20.8 mmol) at 273 K. The reaction mixture was stirred at room temperature for 5 h and then it was poured into an ice-cooled NH₄Cl solution and extracted with CH₂Cl₂ (50 ml) and dried over Na₂SO₄. The reaction mixture was treated with Lawesson's reagent (10.4 mmol) and stirred at room temperature for 5 h. The solvent was removed and the residue was gently heated on steam bath with ethanol. The product was purified by column chromatography (neutral alumina, hexane) to afford compound (I) as a yellow powder. Single crystals of (I) were obtained by recrystallization from boiling hexane.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of (I), viewed approximately down the c axis. Dashed lines indicate C—H···π interactions.

1,3-Bis(4-methoxyphenyl)-2-benzothiophene top

Crystal data top

C₂₂H₁₈O₂S	F(000) = 1456
M_r = 346.42	D_x = 1.330 Mg m⁻³
Orthorhombic, Pcab	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2ac	Cell parameters from 25 reflections
a = 7.508 (6) Å	θ = 1.5–30.0°
b = 16.493 (9) Å	µ = 0.20 mm⁻¹
c = 27.952 (9) Å	T = 293 K
V = 3461 (4) Å³	Block, yellow
Z = 8	0.24 × 0.22 × 0.19 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.000
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 1.5°
Graphite monochromator	h = 0→10
ω scans	k = 0→23
5044 measured reflections	l = 0→39
5044 independent reflections	3 standard reflections every 60 min
3579 reflections with I > 2σ(I)	intensity decay: none

Refinement top

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.235	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1453P)² + 1.73P] where P = (F_o² + 2F_c²)/3
5044 reflections	(Δ/σ)_max = 0.001
228 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₂₂H₁₈O₂S	V = 3461 (4) Å³
M_r = 346.42	Z = 8
Orthorhombic, Pcab	Mo Kα radiation
a = 7.508 (6) Å	µ = 0.20 mm⁻¹
b = 16.493 (9) Å	T = 293 K
c = 27.952 (9) Å	0.24 × 0.22 × 0.19 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.000
5044 measured reflections	3 standard reflections every 60 min
5044 independent reflections	intensity decay: none
3579 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.235	H-atom parameters constrained
S = 1.04	Δρ_max = 0.65 e Å⁻³
5044 reflections	Δρ_min = −0.49 e Å⁻³
228 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.73445 (9)	0.07389 (4)	0.48152 (2)	0.0398 (2)
O1	0.9918 (3)	0.15231 (12)	0.70411 (7)	0.0496 (5)
O2	0.5670 (3)	−0.08331 (12)	0.26912 (7)	0.0535 (5)
C1	0.7680 (3)	0.16315 (14)	0.51128 (9)	0.0355 (5)
C2	0.7421 (3)	0.22830 (14)	0.48059 (9)	0.0345 (5)
C3	0.7623 (3)	0.31269 (14)	0.49035 (10)	0.0389 (5)
H3	0.7987	0.3302	0.5204	0.047*
C4	0.7274 (4)	0.36711 (15)	0.45499 (10)	0.0455 (6)
H4	0.7425	0.4221	0.4612	0.055*
C5	0.6690 (4)	0.34278 (16)	0.40919 (11)	0.0472 (6)
H5	0.6411	0.3819	0.3864	0.057*
C6	0.6530 (4)	0.26293 (15)	0.39783 (10)	0.0424 (6)
H6	0.6174	0.2475	0.3673	0.051*
C7	0.6912 (3)	0.20316 (13)	0.43306 (9)	0.0345 (5)
C8	0.6845 (3)	0.11937 (14)	0.42814 (9)	0.0353 (5)
C9	0.8223 (3)	0.16180 (14)	0.56165 (9)	0.0350 (5)
C10	0.9347 (3)	0.10018 (15)	0.57957 (9)	0.0388 (5)
H10	0.9746	0.0599	0.5589	0.047*
C11	0.9865 (3)	0.09821 (15)	0.62662 (10)	0.0411 (6)
H11	1.0596	0.0567	0.6376	0.049*
C12	0.9296 (3)	0.15848 (14)	0.65786 (9)	0.0368 (5)
C13	0.8177 (3)	0.22008 (15)	0.64162 (9)	0.0382 (5)
H13	0.7792	0.2604	0.6624	0.046*
C14	0.7646 (3)	0.22063 (15)	0.59424 (9)	0.0374 (5)
H14	0.6882	0.2613	0.5837	0.045*
C15	0.9334 (5)	0.21177 (19)	0.73747 (11)	0.0578 (8)
H15A	0.9667	0.2647	0.7263	0.087*
H15B	0.9877	0.2018	0.7680	0.087*
H15C	0.8062	0.2089	0.7406	0.087*
C16	0.6489 (3)	0.06917 (13)	0.38565 (9)	0.0355 (5)
C17	0.5482 (4)	−0.00260 (16)	0.38883 (10)	0.0435 (6)
H17	0.4979	−0.0172	0.4180	0.052*
C18	0.5228 (4)	−0.05154 (16)	0.34961 (11)	0.0451 (6)
H18	0.4551	−0.0985	0.3523	0.054*
C19	0.5986 (3)	−0.03062 (15)	0.30588 (10)	0.0399 (5)
C20	0.6978 (4)	0.03999 (15)	0.30184 (10)	0.0405 (5)
H20	0.7477	0.0545	0.2726	0.049*
C21	0.7222 (3)	0.08870 (15)	0.34164 (9)	0.0393 (5)
H21	0.7895	0.1358	0.3388	0.047*
C22	0.6646 (5)	−0.0704 (2)	0.22628 (12)	0.0594 (8)
H22A	0.6303	−0.0195	0.2124	0.089*
H22B	0.6400	−0.1134	0.2041	0.089*
H22C	0.7897	−0.0695	0.2334	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0468 (4)	0.0279 (3)	0.0448 (4)	0.0002 (2)	−0.0019 (3)	0.0022 (2)
O1	0.0560 (12)	0.0498 (11)	0.0428 (10)	0.0087 (9)	−0.0081 (9)	0.0046 (8)
O2	0.0609 (13)	0.0475 (11)	0.0520 (12)	−0.0088 (9)	−0.0044 (10)	−0.0105 (9)
C1	0.0349 (11)	0.0303 (10)	0.0414 (12)	0.0013 (9)	0.0030 (9)	0.0003 (9)
C2	0.0292 (10)	0.0285 (10)	0.0458 (12)	−0.0004 (8)	0.0022 (9)	−0.0005 (9)
C3	0.0416 (13)	0.0310 (11)	0.0441 (13)	−0.0015 (9)	0.0021 (10)	−0.0035 (9)
C4	0.0554 (16)	0.0299 (11)	0.0512 (15)	0.0002 (11)	0.0066 (12)	−0.0001 (10)
C5	0.0579 (16)	0.0357 (12)	0.0480 (15)	0.0047 (11)	0.0013 (13)	0.0063 (10)
C6	0.0467 (14)	0.0351 (12)	0.0454 (13)	0.0023 (10)	−0.0036 (11)	0.0048 (10)
C7	0.0313 (10)	0.0292 (10)	0.0429 (12)	0.0001 (8)	0.0018 (9)	0.0009 (9)
C8	0.0352 (11)	0.0308 (10)	0.0399 (12)	−0.0012 (9)	0.0010 (9)	0.0005 (9)
C9	0.0296 (10)	0.0315 (10)	0.0439 (12)	−0.0006 (8)	0.0009 (9)	0.0027 (9)
C10	0.0373 (12)	0.0320 (11)	0.0470 (13)	0.0052 (9)	0.0002 (10)	0.0000 (9)
C11	0.0347 (12)	0.0341 (11)	0.0546 (15)	0.0055 (9)	−0.0036 (10)	0.0066 (10)
C12	0.0327 (11)	0.0363 (11)	0.0415 (12)	−0.0027 (9)	−0.0011 (9)	0.0047 (9)
C13	0.0365 (12)	0.0354 (11)	0.0427 (13)	0.0033 (9)	0.0033 (10)	0.0007 (9)
C14	0.0337 (11)	0.0361 (11)	0.0424 (12)	0.0070 (9)	−0.0008 (10)	0.0035 (9)
C15	0.075 (2)	0.0488 (16)	0.0499 (16)	0.0049 (15)	−0.0012 (15)	−0.0007 (13)
C16	0.0341 (11)	0.0300 (10)	0.0425 (12)	0.0004 (8)	−0.0003 (9)	−0.0014 (9)
C17	0.0430 (13)	0.0374 (12)	0.0502 (15)	−0.0078 (10)	0.0079 (11)	0.0002 (10)
C18	0.0421 (13)	0.0375 (12)	0.0556 (15)	−0.0112 (10)	0.0027 (12)	−0.0043 (11)
C19	0.0361 (12)	0.0358 (11)	0.0478 (14)	0.0008 (9)	−0.0073 (10)	−0.0031 (10)
C20	0.0443 (13)	0.0372 (12)	0.0401 (12)	−0.0012 (10)	0.0008 (10)	0.0028 (10)
C21	0.0404 (13)	0.0329 (11)	0.0445 (13)	−0.0041 (9)	0.0010 (10)	0.0002 (9)
C22	0.066 (2)	0.0622 (19)	0.0507 (17)	0.0026 (15)	−0.0043 (15)	−0.0094 (14)

Geometric parameters (Å, º) top

S1—C1	1.710 (3)	C10—H10	0.93
S1—C8	1.712 (3)	C11—C12	1.390 (4)
O1—C12	1.378 (3)	C11—H11	0.93
O1—C15	1.422 (4)	C12—C13	1.394 (3)
O2—C19	1.367 (3)	C13—C14	1.383 (4)
O2—C22	1.420 (4)	C13—H13	0.93
C1—C2	1.389 (3)	C14—H14	0.93
C1—C9	1.466 (4)	C15—H15A	0.96
C2—C3	1.427 (3)	C15—H15B	0.96
C2—C7	1.443 (4)	C15—H15C	0.96
C3—C4	1.361 (4)	C16—C21	1.386 (4)
C3—H3	0.93	C16—C17	1.407 (3)
C4—C5	1.411 (4)	C17—C18	1.375 (4)
C4—H4	0.93	C17—H17	0.93
C5—C6	1.360 (4)	C18—C19	1.392 (4)
C5—H5	0.93	C18—H18	0.93
C6—C7	1.423 (3)	C19—C20	1.387 (4)
C6—H6	0.93	C20—C21	1.384 (4)
C7—C8	1.390 (3)	C20—H20	0.93
C8—C16	1.472 (3)	C21—H21	0.93
C9—C14	1.400 (3)	C22—H22A	0.96
C9—C10	1.413 (3)	C22—H22B	0.96
C10—C11	1.372 (4)	C22—H22C	0.96

C1—S1—C8	94.5 (2)	C11—C12—C13	120.1 (2)
C12—O1—C15	117.3 (2)	C14—C13—C12	119.4 (2)
C19—O2—C22	116.7 (2)	C14—C13—H13	120.3
C2—C1—C9	130.1 (2)	C12—C13—H13	120.3
C2—C1—S1	110.19 (19)	C13—C14—C9	122.0 (2)
C9—C1—S1	119.68 (18)	C13—C14—H14	119.0
C1—C2—C3	128.5 (2)	C9—C14—H14	119.0
C1—C2—C7	112.5 (2)	O1—C15—H15A	109.5
C3—C2—C7	119.0 (2)	O1—C15—H15B	109.5
C4—C3—C2	119.0 (2)	H15A—C15—H15B	109.5
C4—C3—H3	120.5	O1—C15—H15C	109.5
C2—C3—H3	120.5	H15A—C15—H15C	109.5
C3—C4—C5	122.1 (2)	H15B—C15—H15C	109.5
C3—C4—H4	119.0	C21—C16—C17	117.7 (2)
C5—C4—H4	119.0	C21—C16—C8	120.9 (2)
C6—C5—C4	121.0 (3)	C17—C16—C8	121.3 (2)
C6—C5—H5	119.5	C18—C17—C16	121.2 (2)
C4—C5—H5	119.5	C18—C17—H17	119.4
C5—C6—C7	119.4 (3)	C16—C17—H17	119.4
C5—C6—H6	120.3	C17—C18—C19	119.9 (2)
C7—C6—H6	120.3	C17—C18—H18	120.1
C8—C7—C6	127.8 (2)	C19—C18—H18	120.1
C8—C7—C2	112.7 (2)	O2—C19—C20	124.5 (3)
C6—C7—C2	119.4 (2)	O2—C19—C18	115.6 (2)
C7—C8—C16	130.2 (2)	C20—C19—C18	120.0 (2)
C7—C8—S1	109.97 (18)	C21—C20—C19	119.5 (2)
C16—C8—S1	119.77 (18)	C21—C20—H20	120.2
C14—C9—C10	116.9 (2)	C19—C20—H20	120.2
C14—C9—C1	121.9 (2)	C20—C21—C16	121.8 (2)
C10—C9—C1	121.2 (2)	C20—C21—H21	119.1
C11—C10—C9	121.7 (2)	C16—C21—H21	119.1
C11—C10—H10	119.1	O2—C22—H22A	109.5
C9—C10—H10	119.1	O2—C22—H22B	109.5
C10—C11—C12	119.9 (2)	H22A—C22—H22B	109.5
C10—C11—H11	120.1	O2—C22—H22C	109.5
C12—C11—H11	120.1	H22A—C22—H22C	109.5
O1—C12—C11	115.6 (2)	H22B—C22—H22C	109.5
O1—C12—C13	124.3 (2)

C8—S1—C1—C2	−0.28 (19)	C1—C9—C10—C11	180.0 (2)
C8—S1—C1—C9	−178.3 (2)	C9—C10—C11—C12	−0.7 (4)
C9—C1—C2—C3	0.1 (4)	C15—O1—C12—C11	−178.6 (3)
S1—C1—C2—C3	−177.7 (2)	C15—O1—C12—C13	1.8 (4)
C9—C1—C2—C7	179.0 (2)	C10—C11—C12—O1	−178.6 (2)
S1—C1—C2—C7	1.2 (3)	C10—C11—C12—C13	1.0 (4)
C1—C2—C3—C4	−179.1 (3)	O1—C12—C13—C14	179.5 (2)
C7—C2—C3—C4	2.1 (4)	C11—C12—C13—C14	−0.1 (4)
C2—C3—C4—C5	1.1 (4)	C12—C13—C14—C9	−1.2 (4)
C3—C4—C5—C6	−3.1 (5)	C10—C9—C14—C13	1.5 (4)
C4—C5—C6—C7	1.7 (4)	C1—C9—C14—C13	−179.1 (2)
C5—C6—C7—C8	−179.2 (3)	C7—C8—C16—C21	41.7 (4)
C5—C6—C7—C2	1.5 (4)	S1—C8—C16—C21	−135.8 (2)
C1—C2—C7—C8	−1.8 (3)	C7—C8—C16—C17	−142.0 (3)
C3—C2—C7—C8	177.3 (2)	S1—C8—C16—C17	40.5 (3)
C1—C2—C7—C6	177.6 (2)	C21—C16—C17—C18	−0.2 (4)
C3—C2—C7—C6	−3.4 (3)	C8—C16—C17—C18	−176.6 (2)
C6—C7—C8—C16	4.5 (4)	C16—C17—C18—C19	0.5 (4)
C2—C7—C8—C16	−176.2 (2)	C22—O2—C19—C20	9.7 (4)
C6—C7—C8—S1	−177.8 (2)	C22—O2—C19—C18	−170.5 (3)
C2—C7—C8—S1	1.5 (3)	C17—C18—C19—O2	179.5 (2)
C1—S1—C8—C7	−0.7 (2)	C17—C18—C19—C20	−0.7 (4)
C1—S1—C8—C16	177.2 (2)	O2—C19—C20—C21	−179.6 (2)
C2—C1—C9—C14	37.1 (4)	C18—C19—C20—C21	0.7 (4)
S1—C1—C9—C14	−145.3 (2)	C19—C20—C21—C16	−0.4 (4)
C2—C1—C9—C10	−143.5 (3)	C17—C16—C21—C20	0.2 (4)
S1—C1—C9—C10	34.1 (3)	C8—C16—C21—C20	176.6 (2)
C14—C9—C10—C11	−0.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O2ⁱ	0.96	2.52	3.385 (5)	149
C11—H11···Cg1ⁱⁱ	0.93	2.73	3.595 (4)	155
C14—H14···Cg2ⁱⁱⁱ	0.93	2.78	3.550 (4)	141
C18—H18···Cg2^iv	0.93	2.88	3.662 (4)	143

Symmetry codes: (i) −x+3/2, y+1/2, −z+1; (ii) −x+2, −y, −z+1; (iii) x−1/2, −y+1/2, z; (iv) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₁₈O₂S
M_r	346.42
Crystal system, space group	Orthorhombic, Pcab
Temperature (K)	293
a, b, c (Å)	7.508 (6), 16.493 (9), 27.952 (9)
V (Å³)	3461 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.24 × 0.22 × 0.19

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5044, 5044, 3579
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.235, 1.04
No. of reflections	5044
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.49

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

S1—C1	1.710 (3)	O1—C15	1.422 (4)
S1—C8	1.712 (3)	O2—C19	1.367 (3)
O1—C12	1.378 (3)	O2—C22	1.420 (4)

C1—S1—C8	94.5 (2)	C14—C9—C10	116.9 (2)
C12—O1—C15	117.3 (2)	C21—C16—C17	117.7 (2)
C19—O2—C22	116.7 (2)