1,3-Dimethyl­benzo[b]dibenzothio­phene

Umarani, P.R.; Marx, A.; Dhayalan, V.; Mohanakrishnan, A.K.; Manivannan, V.

doi:10.1107/S1600536809003456

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o440

doi:10.1107/S1600536809003456

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1,3-Dimethylbenzo[b]dibenzothiophene

P. R. Umarani,^a A. Marx,^a V. Dhayalan,^b A. K. Mohanakrishnan ^b and V. Manivannan ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: manivan_1999@yahoo.com

(Received 27 January 2009; accepted 28 January 2009; online 31 January 2009)

The molecule of the title compound, C₁₈H₁₄S, is approximately planar (r.m.s. deviation = 0.029 Å). The crystal packing is stabilized by weak intermolecular C—H⋯π interactions.

Related literature

For the pharmacological activities of thiophen derivatives, see: Dzhurayev et al. (1992 ); El-Maghraby et al. (1984 ); Gewald et al. (1996 ). For related structures, see: Harrison et al. (2006 ); Palani et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₈H₁₄S
M_r = 262.35
Monoclinic, P 2₁ /n
a = 10.0219 (3) Å
b = 5.8692 (5) Å
c = 22.8554 (5) Å
β = 99.787 (1)°
V = 1324.80 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 (2) K
0.26 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.944, T_max = 0.961
27929 measured reflections
3030 independent reflections
2574 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.137
S = 1.08
3030 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C9/C14–C16 ring and Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17C⋯Cg1ⁱ	0.96	2.68	3.486 (2)	142
C18—H18A⋯Cg2ⁱⁱ	0.96	2.75	3.649 (3)	155
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003456/bt2861sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003456/bt2861Isup2.hkl

checkCIF report

Comment top

Thiophen derivatives possess pharmacological activities such as anti-bacterial, anti-cancer, anti-inflammatory (El-Maghraby et al., 1984; Dzhurayev et al., 1992) and anti-toxic properties (Gewald et al., 1996).

The geometric parameters of the title molecule (Fig. 1) agree well with related structures (Harrison et al., 2006; Palani et al., 2006) and literature values (Allen et al., 1987). All non-H atoms lie in a common plane (r.m.s. deviation 0.029Å) .

The crystal packing is stabilized by weak intermolecular C - H···π [C17—H17C···Cg1 (1 - x, -y, 1 - z), H17C···Cg1 = 2.68 Å, C18—H18A··· Cg2 (1 + x, y, z), H18A···Cg1 = 2.75 Å; Cg1 and Cg2 are the centroid of rings defined by atoms C7/C8/C9/C14/C15/C16 and C1—C6, respectively) interactions. No significant intra- and intermolecular hydrogen bonds are observed.

Related literature top

For the pharmacological activities of thiophen derivatives, see: Dzhurayev et al. (1992); El-Maghraby et al. (1984); Gewald et al. (1996). For related structures, see: Harrison et al. (2006); Palani et al. (2006). For bond-length data, see: Allen et al. (1987). Cg1 is the centroid of the C7–C9/C14–C16 ring and Cg2 is the centroid of the C1–C6 ring.

Experimental top

To a solution of diethyl 2-((2-(bromomethyl)banzo[b]thiophen-3-yl) methylene)malonate (0.35 g, 0.88 mmol) in dry 1,2-DCE (15 ml), ZnBr₂ (0.39 g, 1.73 mmol) and m-xylene (0.13 ml, 1.03 mmol), were added. The reaction mixture was then refluxed for 2 h under N₂ atmosphere. It was then poured over ice-water (50 ml) containing 2 ml of conc.HCl, extracted with chloroform (3 X 10 ml) and dried (Na₂SO₄). The removal of solvent followed by flash column chromatographic purification (silica gel, 230–420 mesh, n-hexane/ethyl acetate 99:1) afforded 1,3-dimethylbenzo[2,3-b] dibenzothiophene as a colourless crystal.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

1,3-Dimethylbenzo[b]dibenzothiophene top

Crystal data top

C₁₈H₁₄S	F(000) = 552
M_r = 262.35	D_x = 1.315 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6370 reflections
a = 10.0219 (3) Å	θ = 2.1–27.4°
b = 5.8692 (5) Å	µ = 0.23 mm⁻¹
c = 22.8554 (5) Å	T = 295 K
β = 99.787 (1)°	Block, colourless
V = 1324.80 (12) Å³	0.26 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	3030 independent reflections
Radiation source: fine-focus sealed tube	2574 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and ϕ scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.944, T_max = 0.961	k = −7→7
27929 measured reflections	l = −29→29

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0636P)² + 0.5697P] where P = (F_o² + 2F_c²)/3
3030 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₈H₁₄S	V = 1324.80 (12) Å³
M_r = 262.35	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0219 (3) Å	µ = 0.23 mm⁻¹
b = 5.8692 (5) Å	T = 295 K
c = 22.8554 (5) Å	0.26 × 0.20 × 0.18 mm
β = 99.787 (1)°

Data collection top

Bruker Kappa APEXII diffractometer	3030 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2574 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.961	R_int = 0.029
27929 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.08	Δρ_max = 0.26 e Å⁻³
3030 reflections	Δρ_min = −0.29 e Å⁻³
174 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.07838 (18)	−0.0783 (3)	0.33166 (8)	0.0456 (4)
C2	−0.0587 (2)	−0.0829 (4)	0.30694 (10)	0.0567 (5)
H2	−0.1153	−0.1953	0.3177	0.068*
C3	−0.1081 (2)	0.0813 (4)	0.26653 (9)	0.0603 (6)
H3	−0.1993	0.0801	0.2496	0.072*
C4	−0.0245 (2)	0.2490 (4)	0.25047 (9)	0.0579 (5)
H4	−0.0599	0.3589	0.2228	0.069*
C5	0.1110 (2)	0.2546 (3)	0.27511 (8)	0.0494 (5)
H5	0.1667	0.3678	0.2641	0.059*
C6	0.16390 (17)	0.0909 (3)	0.31632 (7)	0.0403 (4)
C7	0.30153 (17)	0.0662 (3)	0.34821 (7)	0.0378 (4)
C8	0.41378 (18)	0.1971 (3)	0.34603 (7)	0.0408 (4)
H8	0.4071	0.3228	0.3209	0.049*
C9	0.53930 (17)	0.1436 (3)	0.38139 (7)	0.0390 (4)
C10	0.65545 (19)	0.2770 (3)	0.37964 (8)	0.0472 (4)
H10	0.6490	0.4027	0.3545	0.057*
C11	0.77693 (19)	0.2268 (3)	0.41376 (9)	0.0480 (4)
C12	0.78456 (18)	0.0376 (3)	0.45225 (8)	0.0477 (4)
H12	0.8674	0.0037	0.4757	0.057*
C13	0.67622 (18)	−0.0979 (3)	0.45659 (8)	0.0419 (4)
C14	0.54908 (17)	−0.0488 (3)	0.41992 (7)	0.0381 (4)
C15	0.43329 (18)	−0.1822 (3)	0.42159 (8)	0.0437 (4)
H15	0.4381	−0.3086	0.4464	0.052*
C16	0.31376 (18)	−0.1253 (3)	0.38656 (8)	0.0418 (4)
C17	0.6892 (2)	−0.2914 (4)	0.49988 (9)	0.0523 (5)
H17A	0.7795	−0.2944	0.5222	0.078*
H17B	0.6709	−0.4324	0.4787	0.078*
H17C	0.6256	−0.2714	0.5265	0.078*
C18	0.9007 (2)	0.3703 (4)	0.41279 (11)	0.0648 (6)
H18A	0.9598	0.2941	0.3902	0.097*
H18B	0.9471	0.3935	0.4527	0.097*
H18C	0.8742	0.5149	0.3949	0.097*
S1	0.16072 (5)	−0.26890 (9)	0.38419 (3)	0.0592 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0419 (9)	0.0449 (10)	0.0474 (9)	−0.0078 (8)	0.0001 (7)	−0.0003 (8)
C2	0.0429 (10)	0.0597 (12)	0.0632 (12)	−0.0153 (9)	−0.0030 (9)	0.0030 (10)
C3	0.0429 (10)	0.0772 (15)	0.0557 (11)	−0.0015 (10)	−0.0060 (8)	−0.0008 (10)
C4	0.0542 (11)	0.0668 (14)	0.0491 (11)	0.0049 (10)	−0.0018 (9)	0.0105 (9)
C5	0.0511 (10)	0.0519 (11)	0.0442 (9)	−0.0012 (8)	0.0053 (8)	0.0069 (8)
C6	0.0406 (9)	0.0429 (9)	0.0367 (8)	−0.0034 (7)	0.0042 (7)	−0.0033 (7)
C7	0.0391 (8)	0.0378 (8)	0.0361 (8)	−0.0034 (7)	0.0054 (6)	−0.0014 (6)
C8	0.0425 (9)	0.0404 (9)	0.0393 (8)	−0.0059 (7)	0.0068 (7)	0.0049 (7)
C9	0.0388 (8)	0.0408 (9)	0.0383 (8)	−0.0050 (7)	0.0089 (6)	−0.0013 (7)
C10	0.0447 (10)	0.0488 (10)	0.0494 (10)	−0.0102 (8)	0.0120 (8)	0.0035 (8)
C11	0.0391 (9)	0.0550 (11)	0.0513 (10)	−0.0108 (8)	0.0116 (8)	−0.0053 (8)
C12	0.0352 (8)	0.0562 (11)	0.0507 (10)	0.0011 (8)	0.0042 (7)	−0.0036 (8)
C13	0.0401 (9)	0.0432 (9)	0.0422 (9)	0.0020 (7)	0.0066 (7)	−0.0026 (7)
C14	0.0387 (8)	0.0371 (9)	0.0386 (8)	−0.0022 (7)	0.0068 (6)	−0.0023 (7)
C15	0.0445 (9)	0.0353 (9)	0.0497 (10)	−0.0051 (7)	0.0036 (7)	0.0050 (7)
C16	0.0417 (9)	0.0364 (9)	0.0461 (9)	−0.0101 (7)	0.0036 (7)	0.0007 (7)
C17	0.0486 (11)	0.0520 (11)	0.0544 (11)	0.0057 (9)	0.0033 (8)	0.0060 (9)
C18	0.0422 (10)	0.0745 (15)	0.0786 (15)	−0.0188 (10)	0.0127 (10)	−0.0002 (12)
S1	0.0460 (3)	0.0503 (3)	0.0749 (4)	−0.0193 (2)	−0.0080 (2)	0.0180 (2)

Geometric parameters (Å, º) top

C1—C2	1.394 (3)	C10—C11	1.362 (3)
C1—C6	1.395 (3)	C10—H10	0.9300
C1—S1	1.7425 (19)	C11—C12	1.411 (3)
C2—C3	1.368 (3)	C11—C18	1.502 (3)
C2—H2	0.9300	C12—C13	1.363 (3)
C3—C4	1.382 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.430 (2)
C4—C5	1.379 (3)	C13—C17	1.497 (3)
C4—H4	0.9300	C14—C15	1.406 (2)
C5—C6	1.386 (3)	C15—C16	1.364 (2)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.454 (2)	C16—S1	1.7428 (17)
C7—C8	1.370 (2)	C17—H17A	0.9600
C7—C16	1.418 (2)	C17—H17B	0.9600
C8—C9	1.410 (2)	C17—H17C	0.9600
C8—H8	0.9300	C18—H18A	0.9600
C9—C10	1.409 (2)	C18—H18B	0.9600
C9—C14	1.425 (2)	C18—H18C	0.9600

C2—C1—C6	121.14 (18)	C10—C11—C18	122.00 (19)
C2—C1—S1	125.84 (16)	C12—C11—C18	119.55 (19)
C6—C1—S1	113.01 (13)	C13—C12—C11	123.04 (17)
C3—C2—C1	118.62 (19)	C13—C12—H12	118.5
C3—C2—H2	120.7	C11—C12—H12	118.5
C1—C2—H2	120.7	C12—C13—C14	118.76 (16)
C2—C3—C4	120.96 (19)	C12—C13—C17	120.64 (17)
C2—C3—H3	119.5	C14—C13—C17	120.59 (16)
C4—C3—H3	119.5	C15—C14—C9	119.19 (16)
C5—C4—C3	120.53 (19)	C15—C14—C13	121.95 (16)
C5—C4—H4	119.7	C9—C14—C13	118.85 (15)
C3—C4—H4	119.7	C16—C15—C14	119.62 (16)
C4—C5—C6	119.81 (19)	C16—C15—H15	120.2
C4—C5—H5	120.1	C14—C15—H15	120.2
C6—C5—H5	120.1	C15—C16—C7	122.13 (16)
C5—C6—C1	118.93 (16)	C15—C16—S1	125.46 (14)
C5—C6—C7	129.09 (17)	C7—C16—S1	112.39 (13)
C1—C6—C7	111.98 (15)	C13—C17—H17A	109.5
C8—C7—C16	118.80 (15)	C13—C17—H17B	109.5
C8—C7—C6	129.86 (16)	H17A—C17—H17B	109.5
C16—C7—C6	111.34 (15)	C13—C17—H17C	109.5
C7—C8—C9	120.82 (16)	H17A—C17—H17C	109.5
C7—C8—H8	119.6	H17B—C17—H17C	109.5
C9—C8—H8	119.6	C11—C18—H18A	109.5
C10—C9—C8	121.39 (16)	C11—C18—H18B	109.5
C10—C9—C14	119.18 (16)	H18A—C18—H18B	109.5
C8—C9—C14	119.43 (15)	C11—C18—H18C	109.5
C11—C10—C9	121.72 (18)	H18A—C18—H18C	109.5
C11—C10—H10	119.1	H18B—C18—H18C	109.5
C9—C10—H10	119.1	C1—S1—C16	91.28 (9)
C10—C11—C12	118.42 (17)

C6—C1—C2—C3	0.7 (3)	C18—C11—C12—C13	178.60 (19)
S1—C1—C2—C3	179.28 (17)	C11—C12—C13—C14	0.9 (3)
C1—C2—C3—C4	−0.1 (3)	C11—C12—C13—C17	−177.74 (17)
C2—C3—C4—C5	−0.2 (4)	C10—C9—C14—C15	−179.87 (16)
C3—C4—C5—C6	0.0 (3)	C8—C9—C14—C15	0.4 (3)
C4—C5—C6—C1	0.6 (3)	C10—C9—C14—C13	1.3 (2)
C4—C5—C6—C7	−179.00 (19)	C8—C9—C14—C13	−178.50 (16)
C2—C1—C6—C5	−0.9 (3)	C12—C13—C14—C15	179.42 (17)
S1—C1—C6—C5	−179.67 (14)	C17—C13—C14—C15	−1.9 (3)
C2—C1—C6—C7	178.73 (18)	C12—C13—C14—C9	−1.7 (3)
S1—C1—C6—C7	0.0 (2)	C17—C13—C14—C9	176.94 (16)
C5—C6—C7—C8	0.2 (3)	C9—C14—C15—C16	−0.2 (3)
C1—C6—C7—C8	−179.43 (18)	C13—C14—C15—C16	178.66 (17)
C5—C6—C7—C16	−179.98 (18)	C14—C15—C16—C7	−0.3 (3)
C1—C6—C7—C16	0.4 (2)	C14—C15—C16—S1	−178.84 (14)
C16—C7—C8—C9	−0.3 (3)	C8—C7—C16—C15	0.5 (3)
C6—C7—C8—C9	179.59 (17)	C6—C7—C16—C15	−179.40 (17)
C7—C8—C9—C10	−179.90 (16)	C8—C7—C16—S1	179.24 (13)
C7—C8—C9—C14	−0.1 (3)	C6—C7—C16—S1	−0.65 (19)
C8—C9—C10—C11	179.83 (18)	C2—C1—S1—C16	−179.0 (2)
C14—C9—C10—C11	0.1 (3)	C6—C1—S1—C16	−0.29 (15)
C9—C10—C11—C12	−0.9 (3)	C15—C16—S1—C1	179.24 (18)
C9—C10—C11—C18	−179.07 (19)	C7—C16—S1—C1	0.54 (14)
C10—C11—C12—C13	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17C···Cg1ⁱ	0.96	2.68	3.486 (2)	142
C18—H18A···Cg2ⁱⁱ	0.96	2.75	3.649 (3)	155

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄S
M_r	262.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	10.0219 (3), 5.8692 (5), 22.8554 (5)
β (°)	99.787 (1)
V (Å³)	1324.80 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.26 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.944, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	27929, 3030, 2574
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.137, 1.08
No. of reflections	3030
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.29

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17C···Cg1ⁱ	0.96	2.68	3.486 (2)	142
C18—H18A···Cg2ⁱⁱ	0.96	2.75	3.649 (3)	155

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, y, z.

References

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Dzhurayev, A. D., Karimkulov, K. M., Makhsumov, A. G. & Amanov, N. (1992). Khim. Farm. Zh. 26, 73–75. CAS Google Scholar
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Volume 65| Part 2| February 2009| Page o440

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