1,2-Bis(1,3-benzothia­zol-2-yl)benzene

Wang, G.; Wu, L.; Zhuang, L.; Wang, J.

doi:10.1107/S1600536808042542

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o158

doi:10.1107/S1600536808042542

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1,2-Bis(1,3-benzothiazol-2-yl)benzene

Guo-wei Wang,^a ^* Lin-ping Wu,^a Ling-hua Zhuang ^b and Jin-tang Wang ^b

^aDepartment of Light Chemical Engineering, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kingwell2004@sina.com.cn

(Received 11 December 2008; accepted 14 December 2008; online 20 December 2008)

The title compound, C₂₀H₁₂N₂S₂, was prepared by the reaction of o-phthalic acid and 2-aminothiophenol under microwave irradation. The phenyl ring, A, and the benzothiazolyl rings, B and C, are planar; the dihedral angles are A/B = 19.9 (11), A/C = 87.8 (3) and B/C = 84.4 (4)°. Weak intermolecular C—H⋯N hydrogen bonds link the molecule, forming zigzag chains parallel to the c axis.

Related literature

For details of the synthesis and applications of benzothiazoles, see: Chakraborti et al. (2004 ); Seijas et al. (2007 ). For the use of microwave-assisted organic synthesis, see: Kappe & Stadler (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₀H₁₂N₂S₂
M_r = 344.44
Monoclinic, P 2₁ /c
a = 10.748 (2) Å
b = 19.148 (4) Å
c = 8.1840 (16) Å
β = 100.77 (3)°
V = 1654.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.909, T_max = 0.968
3000 measured reflections
3000 independent reflections
1640 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.206
S = 1.10
3000 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯N2ⁱ	0.93	2.46	3.370 (7)	165
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808042542/dn2416sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042542/dn2416Isup2.hkl

checkCIF report

Comment top

Benzothiazole are remarkable heterocyclic ring systems. They have been found to exhibit a wide spectrum of biological activities. They have shown antitumor,antimalarial,and fungicide activity. They are also an important class of industrial chemicals. Many kinds of 2-substituted benzothiazoles are utilized as vulcanization accelators in the manufacture of rubber,as fluorescent brightening agents in textile dyeing,and in the leather industry (Chakraborti et al.,2004; Seijas et al.,2007). There are numerous synthetic methods to produce 2-arylbenzothiazoles. The most important ones include the reaction of o-aminothiophenols with benzoic acids or their derivatives (Chakraborti et al.,2004; Seijas et al.,2007). Microwave-assisted organic synthesis (MAOS) is a powerful technique that is being used more and more to accelerate thermal organic reactions (Kappe & Stadler, 2005). We are focusing on Microwave-assisted synthesis of new products of bisbenzothiazole. We here report the crystal structure of the title compound (I).

The phenyl ring A (C8/C9/C13), benzothiazolyl ring B(C1/C2/C6/C7) and benzothiazolyl ring C(C14/C15/C20) are planar (Fig. 1). The dihedral angles between them are A/B = 19.9°, A/C = 87.8°, B/C = 84.4°, respectively. All bond lengths are within normal ranges (Allen et al., 1987). There are weak intermolecular C—H···N hydrogen bonds whick link the molecule forming zig-zag chains parallel to the c axis .(Table 1, Fig.2).

Related literature top

For details of the synthesis and applications of benzothiazoles, see: Chakraborti et al. (2004); Seijas et al. (2007). For the use of microwave-assisted organic synthesis, see: Kappe & Stadler (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 2-aminothiophenol (2.5 g, 20 mmol), 5 ml orthophosphoric acid, 5 g polyphosphoric acid and o-phthalic acid (1.66 g, 10 mmol) in a beakerflask (150 ml) was placed in a domestic microwave oven (0.8 KW, 2450 MHz) and irradiated (micromode, full power) for 4 min(30 s per time). The reaction mixture was cooled to r.t. and washed with aq NaOH (20%, 150 ml), The pH was adjusted to 10, the resulted solide was filtered. Then the crude compound(I) was obtained. It was crystallized from ethanol. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of methanol. ¹H NMR (DMSO, δ, p.p.m.) 7.35–7.40 (m, 2 H), 7.46–7.51 (m, 2 H), 7.64 (dd,2 H), 7.81 (d, 2 H), 7.95 (dd,2 H), 8.05 (d,2 H).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of (I) with the atom-numbering scheme. Ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view of (I) showing the C-H···N hydrogen bonds shown as dashed lines. [Symmetry code: (i) x, -y+1/2, z-1/2 ]

1,2-Bis(1,3-benzothiazol-2-yl)benzene top

Crystal data top

C₂₀H₁₂N₂S₂	F(000) = 712
M_r = 344.44	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27 reflections
a = 10.748 (2) Å	θ = 1–25°
b = 19.148 (4) Å	µ = 0.32 mm⁻¹
c = 8.1840 (16) Å	T = 293 K
β = 100.77 (3)°	Block, yellow
V = 1654.6 (6) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1640 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→22
T_min = 0.909, T_max = 0.968	l = 0→9
3000 measured reflections	3 standard reflections every 200 reflections
3000 independent reflections	intensity decay: 9%

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0773P)² + 1.3256P] where P = (F_o² + 2F_c²)/3
3000 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₀H₁₂N₂S₂	V = 1654.6 (6) Å³
M_r = 344.44	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.748 (2) Å	µ = 0.32 mm⁻¹
b = 19.148 (4) Å	T = 293 K
c = 8.1840 (16) Å	0.30 × 0.20 × 0.10 mm
β = 100.77 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1640 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.909, T_max = 0.968	3 standard reflections every 200 reflections
3000 measured reflections	intensity decay: 9%
3000 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.206	H-atom parameters constrained
S = 1.10	Δρ_max = 0.31 e Å⁻³
3000 reflections	Δρ_min = −0.32 e Å⁻³
217 parameters

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.

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
C1	0.1724 (9)	0.5336 (4)	0.9897 (12)	0.108 (3)
H1	0.1202	0.5630	1.0376	0.130*
C2	0.1344 (7)	0.5137 (4)	0.8270 (9)	0.096 (2)
H2	0.0583	0.5291	0.7640	0.116*
C3	0.2149 (6)	0.4693 (3)	0.7600 (7)	0.0610 (15)
C4	0.3256 (5)	0.4465 (3)	0.8557 (6)	0.0524 (13)
C5	0.3633 (6)	0.4661 (3)	1.0209 (7)	0.0664 (16)
H5	0.4376	0.4496	1.0862	0.080*
C6	0.2832 (8)	0.5121 (4)	1.0827 (9)	0.085 (2)
H6	0.3064	0.5284	1.1911	0.102*
C7	0.2792 (4)	0.4036 (3)	0.5708 (6)	0.0456 (12)
C8	0.2677 (5)	0.3692 (3)	0.4050 (6)	0.0457 (12)
C9	0.1489 (5)	0.3646 (3)	0.3069 (7)	0.0586 (15)
H9	0.0800	0.3835	0.3453	0.070*
C10	0.1297 (6)	0.3325 (3)	0.1532 (8)	0.0712 (18)
H10	0.0485	0.3300	0.0897	0.085*
C11	0.2287 (6)	0.3044 (3)	0.0938 (8)	0.0702 (17)
H11	0.2159	0.2832	−0.0102	0.084*
C12	0.3461 (6)	0.3079 (3)	0.1882 (8)	0.0664 (16)
H12	0.4133	0.2888	0.1464	0.080*
C13	0.3715 (5)	0.3394 (3)	0.3479 (6)	0.0474 (12)
C14	0.5036 (5)	0.3402 (3)	0.4373 (6)	0.0486 (13)
C15	0.6821 (5)	0.3021 (3)	0.5897 (6)	0.0478 (13)
C16	0.7649 (6)	0.2577 (3)	0.6947 (8)	0.0701 (17)
H16	0.7366	0.2153	0.7297	0.084*
C17	0.8887 (6)	0.2782 (4)	0.7449 (8)	0.0744 (18)
H17	0.9447	0.2498	0.8157	0.089*
C18	0.9307 (6)	0.3412 (4)	0.6907 (7)	0.0682 (17)
H18	1.0155	0.3532	0.7240	0.082*
C19	0.8532 (5)	0.3858 (3)	0.5915 (7)	0.0590 (15)
H19	0.8835	0.4280	0.5583	0.071*
C20	0.7256 (4)	0.3666 (3)	0.5396 (6)	0.0470 (12)
N1	0.1893 (4)	0.4454 (2)	0.5978 (5)	0.0545 (12)
N2	0.5565 (4)	0.2888 (2)	0.5286 (5)	0.0538 (11)
S1	0.40034 (14)	0.39075 (8)	0.73836 (18)	0.0629 (5)
S2	0.60337 (13)	0.40998 (7)	0.41671 (19)	0.0594 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.126 (7)	0.104 (7)	0.109 (7)	0.032 (6)	0.056 (6)	−0.017 (5)
C2	0.102 (6)	0.112 (6)	0.083 (5)	0.036 (5)	0.038 (4)	−0.013 (5)
C3	0.071 (4)	0.061 (4)	0.058 (4)	0.003 (3)	0.029 (3)	−0.004 (3)
C4	0.058 (3)	0.054 (3)	0.048 (3)	−0.007 (3)	0.017 (3)	0.000 (3)
C5	0.077 (4)	0.075 (4)	0.048 (3)	−0.020 (3)	0.014 (3)	−0.005 (3)
C6	0.114 (6)	0.085 (5)	0.067 (4)	−0.017 (5)	0.048 (4)	−0.024 (4)
C7	0.038 (3)	0.048 (3)	0.051 (3)	−0.001 (2)	0.010 (2)	0.008 (2)
C8	0.049 (3)	0.041 (3)	0.050 (3)	0.003 (2)	0.016 (2)	0.005 (2)
C9	0.047 (3)	0.073 (4)	0.055 (4)	−0.002 (3)	0.010 (3)	−0.006 (3)
C10	0.057 (4)	0.083 (5)	0.069 (4)	0.000 (3)	−0.001 (3)	0.005 (4)
C11	0.079 (4)	0.068 (4)	0.061 (4)	−0.002 (4)	0.007 (3)	−0.013 (3)
C12	0.072 (4)	0.060 (4)	0.071 (4)	0.007 (3)	0.023 (3)	−0.010 (3)
C13	0.050 (3)	0.042 (3)	0.053 (3)	0.000 (2)	0.017 (2)	−0.003 (2)
C14	0.049 (3)	0.051 (3)	0.052 (3)	0.007 (2)	0.026 (2)	0.004 (3)
C15	0.047 (3)	0.055 (3)	0.045 (3)	0.013 (2)	0.019 (2)	0.009 (2)
C16	0.076 (4)	0.069 (4)	0.072 (4)	0.015 (3)	0.030 (3)	0.023 (3)
C17	0.075 (4)	0.082 (5)	0.069 (4)	0.022 (4)	0.021 (4)	0.013 (4)
C18	0.056 (3)	0.094 (5)	0.055 (4)	0.007 (3)	0.011 (3)	−0.010 (4)
C19	0.059 (3)	0.065 (4)	0.055 (3)	−0.003 (3)	0.016 (3)	−0.005 (3)
C20	0.043 (3)	0.056 (3)	0.045 (3)	0.006 (2)	0.015 (2)	0.005 (2)
N1	0.045 (2)	0.062 (3)	0.057 (3)	0.015 (2)	0.012 (2)	0.000 (2)
N2	0.053 (3)	0.054 (3)	0.058 (3)	−0.002 (2)	0.021 (2)	0.002 (2)
S1	0.0625 (9)	0.0730 (11)	0.0537 (9)	0.0142 (8)	0.0116 (7)	−0.0059 (8)
S2	0.0572 (9)	0.0493 (8)	0.0699 (10)	−0.0033 (7)	0.0072 (7)	0.0119 (7)

Geometric parameters (Å, º) top

C1—C6	1.352 (10)	C10—H10	0.9300
C1—C2	1.372 (10)	C11—C12	1.352 (8)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.395 (8)	C12—C13	1.418 (7)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.369 (7)	C13—C14	1.471 (7)
C3—N1	1.383 (7)	C14—N2	1.301 (6)
C4—C5	1.389 (7)	C14—S2	1.740 (5)
C4—S1	1.730 (5)	C15—N2	1.373 (6)
C5—C6	1.391 (9)	C15—C16	1.402 (7)
C5—H5	0.9300	C15—C20	1.409 (7)
C6—H6	0.9300	C16—C17	1.374 (8)
C7—N1	1.305 (6)	C16—H16	0.9300
C7—C8	1.492 (7)	C17—C18	1.390 (9)
C7—S1	1.723 (5)	C17—H17	0.9300
C8—C9	1.379 (7)	C18—C19	1.352 (8)
C8—C13	1.409 (7)	C18—H18	0.9300
C9—C10	1.381 (8)	C19—C20	1.407 (7)
C9—H9	0.9300	C19—H19	0.9300
C10—C11	1.360 (8)	C20—S2	1.712 (5)

C6—C1—C2	122.1 (7)	C10—C11—H11	120.5
C6—C1—H1	118.9	C11—C12—C13	123.1 (6)
C2—C1—H1	118.9	C11—C12—H12	118.4
C1—C2—C3	117.2 (7)	C13—C12—H12	118.4
C1—C2—H2	121.4	C8—C13—C12	116.7 (5)
C3—C2—H2	121.4	C8—C13—C14	125.5 (5)
C4—C3—N1	116.0 (5)	C12—C13—C14	117.8 (5)
C4—C3—C2	120.4 (6)	N2—C14—C13	123.7 (5)
N1—C3—C2	123.6 (6)	N2—C14—S2	115.2 (4)
C3—C4—C5	122.3 (6)	C13—C14—S2	121.0 (4)
C3—C4—S1	108.9 (4)	N2—C15—C16	125.4 (5)
C5—C4—S1	128.8 (5)	N2—C15—C20	114.4 (4)
C4—C5—C6	115.9 (6)	C16—C15—C20	120.2 (5)
C4—C5—H5	122.0	C17—C16—C15	118.5 (6)
C6—C5—H5	122.0	C17—C16—H16	120.7
C1—C6—C5	121.9 (7)	C15—C16—H16	120.7
C1—C6—H6	119.0	C16—C17—C18	120.5 (6)
C5—C6—H6	119.0	C16—C17—H17	119.8
N1—C7—C8	119.1 (4)	C18—C17—H17	119.8
N1—C7—S1	115.2 (4)	C19—C18—C17	122.6 (6)
C8—C7—S1	125.6 (4)	C19—C18—H18	118.7
C9—C8—C13	119.0 (5)	C17—C18—H18	118.7
C9—C8—C7	117.9 (4)	C18—C19—C20	118.2 (6)
C13—C8—C7	123.0 (4)	C18—C19—H19	120.9
C8—C9—C10	121.6 (5)	C20—C19—H19	120.9
C8—C9—H9	119.2	C19—C20—C15	119.9 (5)
C10—C9—H9	119.2	C19—C20—S2	130.4 (4)
C11—C10—C9	120.5 (6)	C15—C20—S2	109.7 (4)
C11—C10—H10	119.7	C7—N1—C3	110.2 (4)
C9—C10—H10	119.7	C14—N2—C15	111.4 (4)
C12—C11—C10	119.0 (6)	C7—S1—C4	89.6 (3)
C12—C11—H11	120.5	C20—S2—C14	89.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N2ⁱ	0.93	2.46	3.370 (7)	165

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₂N₂S₂
M_r	344.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.748 (2), 19.148 (4), 8.1840 (16)
β (°)	100.77 (3)
V (Å³)	1654.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.909, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	3000, 3000, 1640
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.206, 1.10
No. of reflections	3000
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N2ⁱ	0.93	2.46	3.370 (7)	165.2

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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