8,9-Di­meth­oxy­benzo[b]naphtho­[2,3-d]thio­phene

Hemanathan, K.; Raja, R.; Murugesan, K.S.

doi:10.1107/S2414314618012579

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181257

https://doi.org/10.1107/S2414314618012579

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access

8,9-Dimethoxybenzo[b]naphtho[2,3-d]thiophene

K. Hemanathan,^a R. Raja ^a and K. Sakthi Murugesan ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
^*Correspondence e-mail: ksakthimurugesan2492@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 July 2018; accepted 5 September 2018; online 21 September 2018)

In the title compound, C₁₈H₁₄O₂S, the system of four fused rings is almost planar (r.m.s. deviation = 0.022 Å). The C atoms of the methoxy groups deviate from the mean plane of the ring system by 0.373 (2) and −0.104 (2) Å. In the crystal, very weak aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.9286 (10) Å] may help to establish the packing.

Keywords: crystal structure; thiophene; dimethoxybenzene..

CCDC reference: 1590246

Structure description

Thiophene and thiazole derivatives are known to possess interesting biological properties, such as anticancer activity (Bondock et al., 2010 ; Al-Said et al., 2011 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound (Fig. 1).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

As expected, the thiophene system is essentially planar and subtends dihedral angles with respect to the mean planes through the naphthalene ring system, i.e. the C7–C18 and C1–C6 phenyl rings, of 1.05 (9) and 1.53 (7)°, respectively. The C atoms of the methoxy groups are slightly displaced from their attached benzene ring, as indicated by the C15—C14—O1—C13 and C10—C11—O2—C12 torsion angles of −4.5 (2) and −9.1 (3)°, respectively. In the crystal, very weak aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.9286 (10) Å between inversion-related C7–C9/C16–C18 rings] may help to establish the packing.

Synthesis and crystallization

To a solution of diethyl 2-[(2-(bromomethyl)benzo[b]thiophen-3-yl)methylidene]malonate (0.20 g, 0.50 mmol) and veratrole (1,2-dimethoxybenzene) (0.08 g, 0.55 mmol) in dry dichloroethane (5 ml) was added ZnBr₂ (0.03 g, 0.10 mmol). The reaction mixture was then stirred at room temperature under a nitrogen atmosphere for 4 h. After completion of the reaction (monitored by TLC), it was poured into ice water (30 ml). The organic layer was separated and the aqueous layer was extracted with DCM (2 × 20 ml). The combined organic layer was washed with water (2 × 20 ml) and dried (Na₂SO₄). Removal of the solvent followed by work-up and column chromatography (silica gel; 4% ethyl acetate in hexane) furnished the title compound (0.10 g, 30%) as a colourless solid (m.p. 463–465 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₈H₁₄O₂S
M_r	294.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.0062 (9), 5.9631 (4), 18.3801 (14)
β (°)	104.019 (7)
V (Å³)	1383.05 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan
T_min, T_max	0.932, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	6823, 3192, 2344
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.119, 1.07
No. of reflections	3192
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.44
Computer programs: APEX2 (Bruker, 2008 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 (Farrugia, 2012 ), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1590246

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618012579/hb4248sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012579/hb4248Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

8,9-Dimethoxybenzo[b]naphtho[2,3-d]thiophene top

Crystal data top

C₁₈H₁₄O₂S	F(000) = 616
M_r = 294.35	D_x = 1.414 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.0062 (9) Å	Cell parameters from 2344 reflections
b = 5.9631 (4) Å	θ = 3.8–29.1°
c = 18.3801 (14) Å	µ = 0.24 mm⁻¹
β = 104.019 (7)°	T = 293 K
V = 1383.05 (17) Å³	Colourless, block
Z = 4	0.30 × 0.30 × 0.25 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2344 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.028
Absorption correction: multi-scan	θ_max = 29.1°, θ_min = 3.8°
T_min = 0.932, T_max = 0.943	h = −17→17
6823 measured reflections	k = −8→7
3192 independent reflections	l = −23→22

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0564P)² + 0.0382P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3192 reflections	Δρ_max = 0.26 e Å⁻³
192 parameters	Δρ_min = −0.44 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
S1	0.71269 (4)	0.65668 (8)	0.07885 (3)	0.04428 (18)
C7	0.63867 (13)	1.0145 (3)	0.13423 (9)	0.0299 (4)
C8	0.56269 (13)	1.1552 (3)	0.15027 (9)	0.0307 (4)
H8	0.583331	1.286299	0.177266	0.037*
O1	0.13171 (9)	0.9465 (2)	0.05384 (7)	0.0436 (3)
O2	0.18546 (9)	1.2955 (2)	0.13568 (8)	0.0448 (3)
C16	0.42315 (13)	0.9019 (3)	0.08384 (9)	0.0306 (4)
C6	0.75384 (13)	1.0333 (3)	0.15487 (9)	0.0311 (4)
C17	0.50106 (13)	0.7594 (3)	0.06797 (10)	0.0361 (4)
H17	0.481504	0.627975	0.040908	0.043*
C15	0.31383 (13)	0.8491 (3)	0.05877 (10)	0.0344 (4)
H15	0.293603	0.720126	0.030484	0.041*
C14	0.23822 (13)	0.9833 (3)	0.07530 (9)	0.0321 (4)
C9	0.45404 (13)	1.1018 (3)	0.12604 (9)	0.0296 (4)
C10	0.37291 (13)	1.2380 (3)	0.14356 (9)	0.0322 (4)
H10	0.391553	1.368253	0.171457	0.039*
C18	0.60588 (13)	0.8151 (3)	0.09257 (10)	0.0324 (4)
C11	0.26907 (14)	1.1807 (3)	0.12021 (10)	0.0324 (4)
C1	0.80319 (13)	0.8525 (3)	0.12815 (10)	0.0352 (4)
C4	0.92672 (15)	1.1857 (3)	0.20944 (11)	0.0456 (5)
H4	0.968898	1.296438	0.237431	0.055*
C2	0.91295 (14)	0.8391 (3)	0.14075 (11)	0.0442 (5)
H2	0.944654	0.718409	0.122655	0.053*
C5	0.81721 (14)	1.1985 (3)	0.19670 (10)	0.0387 (4)
H5	0.786216	1.317639	0.216149	0.046*
C13	0.09704 (14)	0.7594 (3)	0.00580 (11)	0.0457 (5)
H13A	0.127027	0.768290	−0.036975	0.069*
H13B	0.021131	0.760951	−0.010592	0.069*
H13C	0.119651	0.622921	0.032647	0.069*
C12	0.21008 (15)	1.4723 (3)	0.18900 (12)	0.0471 (5)
H12A	0.251238	1.414300	0.235742	0.071*
H12B	0.145632	1.536265	0.196376	0.071*
H12C	0.249993	1.585695	0.170861	0.071*
C3	0.97356 (15)	1.0083 (4)	0.18057 (11)	0.0475 (5)
H3	1.046885	1.003689	0.188240	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0379 (3)	0.0404 (3)	0.0547 (3)	0.0074 (2)	0.0116 (2)	−0.0117 (2)
C7	0.0330 (9)	0.0315 (9)	0.0252 (8)	0.0021 (7)	0.0070 (7)	0.0002 (7)
C8	0.0342 (9)	0.0275 (8)	0.0298 (9)	−0.0006 (7)	0.0067 (7)	−0.0033 (7)
O1	0.0292 (6)	0.0453 (7)	0.0542 (8)	−0.0016 (5)	0.0062 (6)	−0.0118 (6)
O2	0.0354 (7)	0.0431 (7)	0.0573 (9)	0.0049 (6)	0.0137 (6)	−0.0145 (6)
C16	0.0314 (9)	0.0294 (8)	0.0309 (9)	0.0008 (7)	0.0074 (7)	−0.0027 (7)
C6	0.0319 (9)	0.0365 (9)	0.0252 (8)	0.0014 (7)	0.0078 (7)	0.0023 (7)
C17	0.0375 (10)	0.0306 (9)	0.0390 (10)	0.0019 (8)	0.0067 (8)	−0.0104 (8)
C15	0.0347 (9)	0.0319 (9)	0.0353 (9)	−0.0012 (7)	0.0063 (8)	−0.0081 (7)
C14	0.0307 (9)	0.0327 (9)	0.0316 (9)	−0.0003 (7)	0.0053 (7)	0.0016 (7)
C9	0.0339 (9)	0.0283 (8)	0.0269 (8)	0.0011 (7)	0.0079 (7)	−0.0015 (7)
C10	0.0360 (9)	0.0288 (9)	0.0321 (9)	0.0021 (7)	0.0088 (7)	−0.0044 (7)
C18	0.0337 (9)	0.0308 (9)	0.0330 (9)	0.0048 (7)	0.0090 (7)	−0.0025 (7)
C11	0.0347 (9)	0.0313 (9)	0.0327 (9)	0.0063 (7)	0.0110 (7)	0.0008 (7)
C1	0.0349 (9)	0.0383 (10)	0.0332 (9)	0.0045 (7)	0.0099 (8)	0.0035 (8)
C4	0.0376 (10)	0.0595 (13)	0.0368 (10)	−0.0082 (9)	0.0033 (8)	−0.0015 (9)
C2	0.0377 (10)	0.0525 (12)	0.0444 (11)	0.0104 (9)	0.0138 (9)	0.0041 (9)
C5	0.0364 (10)	0.0482 (11)	0.0311 (9)	0.0016 (8)	0.0074 (8)	−0.0031 (8)
C13	0.0369 (10)	0.0452 (11)	0.0494 (11)	−0.0032 (9)	−0.0007 (9)	−0.0052 (10)
C12	0.0516 (12)	0.0414 (11)	0.0515 (12)	0.0096 (9)	0.0185 (10)	−0.0096 (9)
C3	0.0324 (9)	0.0685 (14)	0.0403 (11)	0.0019 (10)	0.0066 (8)	0.0068 (10)

Geometric parameters (Å, º) top

S1—C1	1.7475 (18)	C15—H15	0.9300
S1—C18	1.7481 (17)	C14—C11	1.438 (2)
C7—C8	1.382 (2)	C9—C10	1.429 (2)
C7—C18	1.422 (2)	C10—C11	1.358 (2)
C7—C6	1.458 (2)	C10—H10	0.9300
C8—C9	1.411 (2)	C1—C2	1.392 (2)
C8—H8	0.9300	C4—C5	1.388 (2)
O1—C14	1.3631 (19)	C4—C3	1.389 (3)
O1—C13	1.427 (2)	C4—H4	0.9300
O2—C11	1.3720 (19)	C2—C3	1.377 (3)
O2—C12	1.422 (2)	C2—H2	0.9300
C16—C17	1.406 (2)	C5—H5	0.9300
C16—C15	1.420 (2)	C13—H13A	0.9600
C16—C9	1.426 (2)	C13—H13B	0.9600
C6—C5	1.391 (2)	C13—H13C	0.9600
C6—C1	1.403 (2)	C12—H12A	0.9600
C17—C18	1.369 (2)	C12—H12B	0.9600
C17—H17	0.9300	C12—H12C	0.9600
C15—C14	1.358 (2)	C3—H3	0.9300

C1—S1—C18	91.32 (8)	C7—C18—S1	112.60 (12)
C8—C7—C18	119.06 (15)	C10—C11—O2	125.90 (15)
C8—C7—C6	129.84 (15)	C10—C11—C14	120.35 (15)
C18—C7—C6	111.08 (14)	O2—C11—C14	113.74 (14)
C7—C8—C9	120.59 (15)	C2—C1—C6	121.58 (17)
C7—C8—H8	119.7	C2—C1—S1	125.64 (14)
C9—C8—H8	119.7	C6—C1—S1	112.78 (13)
C14—O1—C13	116.85 (13)	C5—C4—C3	120.30 (18)
C11—O2—C12	117.09 (13)	C5—C4—H4	119.9
C17—C16—C15	120.92 (15)	C3—C4—H4	119.9
C17—C16—C9	119.72 (15)	C3—C2—C1	118.58 (17)
C15—C16—C9	119.35 (15)	C3—C2—H2	120.7
C5—C6—C1	118.54 (16)	C1—C2—H2	120.7
C5—C6—C7	129.23 (15)	C4—C5—C6	120.05 (17)
C1—C6—C7	112.22 (15)	C4—C5—H5	120.0
C18—C17—C16	119.64 (15)	C6—C5—H5	120.0
C18—C17—H17	120.2	O1—C13—H13A	109.5
C16—C17—H17	120.2	O1—C13—H13B	109.5
C14—C15—C16	121.27 (15)	H13A—C13—H13B	109.5
C14—C15—H15	119.4	O1—C13—H13C	109.5
C16—C15—H15	119.4	H13A—C13—H13C	109.5
C15—C14—O1	125.49 (15)	H13B—C13—H13C	109.5
C15—C14—C11	119.62 (15)	O2—C12—H12A	109.5
O1—C14—C11	114.88 (14)	O2—C12—H12B	109.5
C8—C9—C16	119.28 (15)	H12A—C12—H12B	109.5
C8—C9—C10	122.57 (14)	O2—C12—H12C	109.5
C16—C9—C10	118.13 (15)	H12A—C12—H12C	109.5
C11—C10—C9	121.20 (15)	H12B—C12—H12C	109.5
C11—C10—H10	119.4	C2—C3—C4	120.91 (18)
C9—C10—H10	119.4	C2—C3—H3	119.5
C17—C18—C7	121.70 (15)	C4—C3—H3	119.5
C17—C18—S1	125.70 (13)

C18—C7—C8—C9	0.3 (2)	C8—C7—C18—S1	−179.18 (12)
C6—C7—C8—C9	−178.41 (16)	C6—C7—C18—S1	−0.24 (18)
C8—C7—C6—C5	0.4 (3)	C1—S1—C18—C17	−179.24 (17)
C18—C7—C6—C5	−178.38 (17)	C1—S1—C18—C7	−0.07 (14)
C8—C7—C6—C1	179.31 (17)	C9—C10—C11—O2	178.01 (15)
C18—C7—C6—C1	0.5 (2)	C9—C10—C11—C14	−1.7 (3)
C15—C16—C17—C18	179.70 (16)	C12—O2—C11—C10	−9.1 (3)
C9—C16—C17—C18	−0.6 (3)	C12—O2—C11—C14	170.64 (15)
C17—C16—C15—C14	178.51 (16)	C15—C14—C11—C10	2.6 (2)
C9—C16—C15—C14	−1.1 (3)	O1—C14—C11—C10	−178.48 (16)
C16—C15—C14—O1	−179.95 (16)	C15—C14—C11—O2	−177.11 (15)
C16—C15—C14—C11	−1.2 (3)	O1—C14—C11—O2	1.8 (2)
C13—O1—C14—C15	−4.5 (2)	C5—C6—C1—C2	−1.9 (3)
C13—O1—C14—C11	176.69 (15)	C7—C6—C1—C2	179.11 (15)
C7—C8—C9—C16	−0.8 (2)	C5—C6—C1—S1	178.45 (13)
C7—C8—C9—C10	177.72 (15)	C7—C6—C1—S1	−0.57 (18)
C17—C16—C9—C8	1.0 (2)	C18—S1—C1—C2	−179.29 (16)
C15—C16—C9—C8	−179.36 (15)	C18—S1—C1—C6	0.37 (14)
C17—C16—C9—C10	−177.62 (15)	C6—C1—C2—C3	0.1 (3)
C15—C16—C9—C10	2.0 (2)	S1—C1—C2—C3	179.73 (14)
C8—C9—C10—C11	−179.17 (16)	C3—C4—C5—C6	0.0 (3)
C16—C9—C10—C11	−0.6 (2)	C1—C6—C5—C4	1.8 (3)
C16—C17—C18—C7	0.1 (3)	C7—C6—C5—C4	−179.37 (17)
C16—C17—C18—S1	179.24 (13)	C1—C2—C3—C4	1.8 (3)
C8—C7—C18—C17	0.0 (3)	C5—C4—C3—C2	−1.8 (3)
C6—C7—C18—C17	178.97 (16)

Acknowledgements

The authors thank the Department of Chemistry, Pondicherry University, India, for X-ray intensity data collection.

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