2,2′-Hexamethyl­enedi-1,3-benzothia­zole

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

doi:10.1107/S1600536809000610

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o293

doi:10.1107/S1600536809000610

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2,2′-Hexamethylenedi-1,3-benzothiazole

Guo-wei Wang,^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 22 December 2008; accepted 7 January 2009; online 14 January 2009)

The title compound, C₂₀H₂₀N₂S₂, was prepared by the reaction of suberic acid and 2-aminothiophenol under microwave irradiation. The molecule lies on an inversion center.

Related literature

For details of the synthesis and the application of benzothiazoles, see: Chakraborti et al. (2004 ); Seijas et al. (2007 ); Wang et al. (2009 ). For the use of microwave-assisted organic synthesis, see: Kappe & Stadler (2005 ).

Experimental

Crystal data

C₂₀H₂₀N₂S₂
M_r = 342.50
Monoclinic, P 2₁ /n
a = 5.7590 (12) Å
b = 8.3030 (17) Å
c = 18.974 (4) Å
β = 96.03 (3)°
V = 902.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.30 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 = 0.916, T_max = 0.971
1626 measured reflections
1626 independent reflections
1102 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.182
S = 1.01
1626 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.40 e Å⁻³

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000610/bx2191sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000610/bx2191Isup2.hkl

checkCIF report

Comment top

Benzothiazole are remarkable heterocyclic ring systems. They have been found to exhibit a wide spectrum of biological activities. 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; Wang et al., 2009). 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; Wang et al., 2009). 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 atom-numbering scheme of (I) is shown in Fig. 1.The compound lies on an inversion center (symmetry code -x+1, -y, -z ).

Related literature top

For details of the synthesis procedure and the application of benzothiazoles, see: Chakraborti et al. (2004); Seijas et al. (2007); Wang et al. (2009). For the use of microwave-assisted organic synthesis, see: Kappe & Stadler (2005).

Experimental top

A mixture of 2-aminothiophenol (2.5 g, 20 mmol), 5 ml orthophosphoric acid, 5 g polyphosphoric acid and 1,6-hexanedicarboxylic acid (1.74 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme and 30% displacement ellipsoids. Unlabeled atoms are related to labeled atoms by symmetry code (-x+1, -y, -z).

2,2'-Hexamethylenedi-1,3-benzothiazole top

Crystal data top

C₂₀H₂₀N₂S₂	F(000) = 372
M_r = 342.50	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 27 reflections
a = 5.7590 (12) Å	θ = 1–25°
b = 8.3030 (17) Å	µ = 0.30 mm⁻¹
c = 18.974 (4) Å	T = 293 K
β = 96.03 (3)°	Block, yellow
V = 902.3 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1102 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 2.2°
ω/2θ scans	h = −6→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.916, T_max = 0.971	l = 0→22
1626 measured reflections	3 standard reflections every 200 reflections
1626 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.06P)² + 1.95P] where P = (F_o² + 2F_c²)/3
1626 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₀H₂₀N₂S₂	V = 902.3 (3) Å³
M_r = 342.50	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.7590 (12) Å	µ = 0.30 mm⁻¹
b = 8.3030 (17) Å	T = 293 K
c = 18.974 (4) Å	0.30 × 0.20 × 0.10 mm
β = 96.03 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1102 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.916, T_max = 0.971	3 standard reflections every 200 reflections
1626 measured reflections	intensity decay: 9%
1626 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.01	Δρ_max = 0.37 e Å⁻³
1626 reflections	Δρ_min = −0.40 e Å⁻³
109 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
S	0.21252 (19)	0.52096 (15)	0.08482 (6)	0.0614 (4)
N	0.6060 (6)	0.5674 (4)	0.16015 (18)	0.0569 (9)
C1	0.0926 (8)	0.8256 (6)	0.1352 (3)	0.0701 (13)
H1A	−0.0542	0.8244	0.1096	0.084*
C2	0.1629 (9)	0.9538 (6)	0.1788 (3)	0.0738 (14)
H2A	0.0601	1.0387	0.1831	0.089*
C3	0.3826 (9)	0.9590 (6)	0.2162 (2)	0.0673 (13)
H3A	0.4266	1.0481	0.2442	0.081*
C4	0.5351 (8)	0.8342 (5)	0.2123 (2)	0.0573 (11)
H4A	0.6813	0.8370	0.2382	0.069*
C5	0.4707 (7)	0.7038 (5)	0.1695 (2)	0.0468 (9)
C6	0.2468 (7)	0.6990 (5)	0.1308 (2)	0.0539 (10)
C7	0.4953 (7)	0.4647 (5)	0.1187 (2)	0.0495 (9)
C8	0.5905 (8)	0.3044 (5)	0.1000 (2)	0.0631 (12)
H8A	0.7463	0.3214	0.0864	0.076*
H8B	0.6065	0.2391	0.1426	0.076*
C9	0.4567 (8)	0.2091 (5)	0.0429 (2)	0.0556 (10)
H9A	0.4414	0.2725	−0.0002	0.067*
H9B	0.3009	0.1901	0.0562	0.067*
C10	0.5656 (8)	0.0488 (5)	0.0278 (2)	0.0583 (11)
H10A	0.7206	0.0683	0.0139	0.070*
H10B	0.5836	−0.0134	0.0712	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0522 (7)	0.0655 (8)	0.0654 (7)	−0.0031 (5)	0.0018 (5)	−0.0103 (6)
N	0.063 (2)	0.056 (2)	0.051 (2)	−0.0014 (17)	0.0036 (16)	−0.0028 (17)
C1	0.061 (3)	0.075 (3)	0.076 (3)	0.008 (2)	0.018 (2)	0.002 (3)
C2	0.084 (4)	0.065 (3)	0.078 (3)	0.013 (3)	0.035 (3)	−0.007 (3)
C3	0.088 (4)	0.061 (3)	0.058 (3)	−0.011 (3)	0.031 (2)	−0.013 (2)
C4	0.067 (3)	0.063 (3)	0.043 (2)	−0.014 (2)	0.0089 (19)	−0.011 (2)
C5	0.057 (2)	0.044 (2)	0.040 (2)	−0.0024 (17)	0.0089 (17)	0.0032 (17)
C6	0.050 (2)	0.066 (3)	0.047 (2)	−0.006 (2)	0.0127 (18)	−0.006 (2)
C7	0.055 (2)	0.047 (2)	0.046 (2)	−0.0056 (18)	0.0063 (17)	−0.0045 (18)
C8	0.070 (3)	0.053 (3)	0.066 (3)	0.009 (2)	0.005 (2)	0.007 (2)
C9	0.067 (3)	0.052 (2)	0.048 (2)	−0.002 (2)	0.0086 (19)	0.0016 (19)
C10	0.071 (3)	0.053 (2)	0.052 (2)	0.007 (2)	0.012 (2)	0.002 (2)

Geometric parameters (Å, º) top

S—C6	1.717 (4)	C4—H4A	0.9300
S—C7	1.750 (4)	C5—C6	1.416 (5)
N—C7	1.283 (5)	C7—C8	1.496 (6)
N—C5	1.397 (5)	C8—C9	1.489 (6)
C1—C2	1.382 (7)	C8—H8A	0.9700
C1—C6	1.384 (6)	C8—H8B	0.9700
C1—H1A	0.9300	C9—C10	1.512 (6)
C2—C3	1.385 (7)	C9—H9A	0.9700
C2—H2A	0.9300	C9—H9B	0.9700
C3—C4	1.365 (6)	C10—C10ⁱ	1.473 (8)
C3—H3A	0.9300	C10—H10A	0.9700
C4—C5	1.380 (5)	C10—H10B	0.9700

C6—S—C7	89.46 (19)	N—C7—S	115.5 (3)
C7—N—C5	111.6 (4)	C8—C7—S	120.0 (3)
C2—C1—C6	118.1 (5)	C9—C8—C7	118.1 (4)
C2—C1—H1A	120.9	C9—C8—H8A	107.8
C6—C1—H1A	120.9	C7—C8—H8A	107.8
C1—C2—C3	121.7 (5)	C9—C8—H8B	107.8
C1—C2—H2A	119.2	C7—C8—H8B	107.8
C3—C2—H2A	119.2	H8A—C8—H8B	107.1
C4—C3—C2	120.4 (4)	C8—C9—C10	114.4 (4)
C4—C3—H3A	119.8	C8—C9—H9A	108.7
C2—C3—H3A	119.8	C10—C9—H9A	108.7
C3—C4—C5	119.5 (4)	C8—C9—H9B	108.7
C3—C4—H4A	120.2	C10—C9—H9B	108.7
C5—C4—H4A	120.2	H9A—C9—H9B	107.6
C4—C5—N	126.3 (4)	C10ⁱ—C10—C9	115.4 (5)
C4—C5—C6	120.1 (4)	C10ⁱ—C10—H10A	108.4
N—C5—C6	113.6 (4)	C9—C10—H10A	108.4
C1—C6—C5	120.1 (4)	C10ⁱ—C10—H10B	108.4
C1—C6—S	130.1 (4)	C9—C10—H10B	108.4
C5—C6—S	109.7 (3)	H10A—C10—H10B	107.5
N—C7—C8	124.4 (4)

C6—C1—C2—C3	1.3 (7)	N—C5—C6—S	0.9 (4)
C1—C2—C3—C4	−1.6 (7)	C7—S—C6—C1	−179.0 (5)
C2—C3—C4—C5	1.3 (7)	C7—S—C6—C5	−0.5 (3)
C3—C4—C5—N	−179.7 (4)	C5—N—C7—C8	−178.0 (4)
C3—C4—C5—C6	−0.8 (6)	C5—N—C7—S	0.5 (5)
C7—N—C5—C4	178.0 (4)	C6—S—C7—N	0.0 (3)
C7—N—C5—C6	−0.9 (5)	C6—S—C7—C8	178.6 (4)
C2—C1—C6—C5	−0.8 (7)	N—C7—C8—C9	−170.9 (4)
C2—C1—C6—S	177.5 (4)	S—C7—C8—C9	10.6 (6)
C4—C5—C6—C1	0.5 (6)	C7—C8—C9—C10	−179.9 (4)
N—C5—C6—C1	179.6 (4)	C8—C9—C10—C10ⁱ	179.1 (5)
C4—C5—C6—S	−178.1 (3)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₂S₂
M_r	342.50
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.7590 (12), 8.3030 (17), 18.974 (4)
β (°)	96.03 (3)
V (Å³)	902.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
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	0.916, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	1626, 1626, 1102
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.182, 1.01
No. of reflections	1626
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.40

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

References

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