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Acta Cryst. (2009). E65, o293    [ doi:10.1107/S1600536809000610 ]

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

G. Wang, L. Zhuang and J. Wang

Abstract top

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.

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).

Refinement top

All H atoms were positioned geometrically, with C—H = 0.93 and 0.97 Å for methyl and methylene H atoms, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x= 1.5 for methyl H and x = 1.2 for methylene H atoms.

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
[Figure 1] 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
C20H20N2S2F(000) = 372
Mr = 342.50Dx = 1.297 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 27 reflections
a = 5.7590 (12) Åθ = 1–25°
b = 8.3030 (17) ŵ = 0.30 mm−1
c = 18.974 (4) ÅT = 293 K
β = 96.03 (3)°Block, yellow
V = 902.3 (3) Å30.30 × 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 tubeRint = 0.0000
graphiteθmax = 25.3°, θmin = 2.2°
ω/2θ scansh = −6→6
Absorption correction: ψ scan
(North et al., 1968)		k = 0→9
Tmin = 0.916, Tmax = 0.971l = 0→22
1626 measured reflections3 standard reflections every 200 reflections
1626 independent reflections intensity decay: 9%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.06P)2 + 1.95P]
where P = (Fo2 + 2Fc2)/3
1626 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.37 e Å−3
0 restraintsΔρmin = −0.39 e Å−3
Crystal data top
C20H20N2S2V = 902.3 (3) Å3
Mr = 342.50Z = 2
Monoclinic, P21/nMo Kα radiation
a = 5.7590 (12) ŵ = 0.30 mm−1
b = 8.3030 (17) ÅT = 293 K
c = 18.974 (4) Å0.30 × 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)		Rint = 0.0000
Tmin = 0.916, Tmax = 0.971θmax = 25.3°
1626 measured reflections3 standard reflections every 200 reflections
1626 independent reflections intensity decay: 9%
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.182Δρmax = 0.37 e Å−3
S = 1.01Δρmin = −0.39 e Å−3
1626 reflectionsAbsolute structure: ?
109 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
S0.21252 (19)0.52096 (15)0.08482 (6)0.0614 (4)
N0.6060 (6)0.5674 (4)0.16015 (18)0.0569 (9)
C10.0926 (8)0.8256 (6)0.1352 (3)0.0701 (13)
H1A−0.05420.82440.10960.084*
C20.1629 (9)0.9538 (6)0.1788 (3)0.0738 (14)
H2A0.06011.03870.18310.089*
C30.3826 (9)0.9590 (6)0.2162 (2)0.0673 (13)
H3A0.42661.04810.24420.081*
C40.5351 (8)0.8342 (5)0.2123 (2)0.0573 (11)
H4A0.68130.83700.23820.069*
C50.4707 (7)0.7038 (5)0.1695 (2)0.0468 (9)
C60.2468 (7)0.6990 (5)0.1308 (2)0.0539 (10)
C70.4953 (7)0.4647 (5)0.1187 (2)0.0495 (9)
C80.5905 (8)0.3044 (5)0.1000 (2)0.0631 (12)
H8A0.74630.32140.08640.076*
H8B0.60650.23910.14260.076*
C90.4567 (8)0.2091 (5)0.0429 (2)0.0556 (10)
H9A0.44140.2725−0.00020.067*
H9B0.30090.19010.05620.067*
C100.5656 (8)0.0488 (5)0.0278 (2)0.0583 (11)
H10A0.72060.06830.01390.070*
H10B0.5836−0.01340.07120.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S0.0522 (7)0.0655 (8)0.0654 (7)−0.0031 (5)0.0018 (5)−0.0103 (6)
N0.063 (2)0.056 (2)0.051 (2)−0.0014 (17)0.0036 (16)−0.0028 (17)
C10.061 (3)0.075 (3)0.076 (3)0.008 (2)0.018 (2)0.002 (3)
C20.084 (4)0.065 (3)0.078 (3)0.013 (3)0.035 (3)−0.007 (3)
C30.088 (4)0.061 (3)0.058 (3)−0.011 (3)0.031 (2)−0.013 (2)
C40.067 (3)0.063 (3)0.043 (2)−0.014 (2)0.0089 (19)−0.011 (2)
C50.057 (2)0.044 (2)0.040 (2)−0.0024 (17)0.0089 (17)0.0032 (17)
C60.050 (2)0.066 (3)0.047 (2)−0.006 (2)0.0127 (18)−0.006 (2)
C70.055 (2)0.047 (2)0.046 (2)−0.0056 (18)0.0063 (17)−0.0045 (18)
C80.070 (3)0.053 (3)0.066 (3)0.009 (2)0.005 (2)0.007 (2)
C90.067 (3)0.052 (2)0.048 (2)−0.002 (2)0.0086 (19)0.0016 (19)
C100.071 (3)0.053 (2)0.052 (2)0.007 (2)0.012 (2)0.002 (2)
Geometric parameters (Å, °) top
S—C61.717 (4)C4—H4A0.9300
S—C71.750 (4)C5—C61.416 (5)
N—C71.283 (5)C7—C81.496 (6)
N—C51.397 (5)C8—C91.489 (6)
C1—C21.382 (7)C8—H8A0.9700
C1—C61.384 (6)C8—H8B0.9700
C1—H1A0.9300C9—C101.512 (6)
C2—C31.385 (7)C9—H9A0.9700
C2—H2A0.9300C9—H9B0.9700
C3—C41.365 (6)C10—C10i1.473 (8)
C3—H3A0.9300C10—H10A0.9700
C4—C51.380 (5)C10—H10B0.9700
C6—S—C789.46 (19)N—C7—S115.5 (3)
C7—N—C5111.6 (4)C8—C7—S120.0 (3)
C2—C1—C6118.1 (5)C9—C8—C7118.1 (4)
C2—C1—H1A120.9C9—C8—H8A107.8
C6—C1—H1A120.9C7—C8—H8A107.8
C1—C2—C3121.7 (5)C9—C8—H8B107.8
C1—C2—H2A119.2C7—C8—H8B107.8
C3—C2—H2A119.2H8A—C8—H8B107.1
C4—C3—C2120.4 (4)C8—C9—C10114.4 (4)
C4—C3—H3A119.8C8—C9—H9A108.7
C2—C3—H3A119.8C10—C9—H9A108.7
C3—C4—C5119.5 (4)C8—C9—H9B108.7
C3—C4—H4A120.2C10—C9—H9B108.7
C5—C4—H4A120.2H9A—C9—H9B107.6
C4—C5—N126.3 (4)C10i—C10—C9115.4 (5)
C4—C5—C6120.1 (4)C10i—C10—H10A108.4
N—C5—C6113.6 (4)C9—C10—H10A108.4
C1—C6—C5120.1 (4)C10i—C10—H10B108.4
C1—C6—S130.1 (4)C9—C10—H10B108.4
C5—C6—S109.7 (3)H10A—C10—H10B107.5
N—C7—C8124.4 (4)
C6—C1—C2—C31.3 (7)N—C5—C6—S0.9 (4)
C1—C2—C3—C4−1.6 (7)C7—S—C6—C1−179.0 (5)
C2—C3—C4—C51.3 (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—S0.5 (5)
C7—N—C5—C4178.0 (4)C6—S—C7—N0.0 (3)
C7—N—C5—C6−0.9 (5)C6—S—C7—C8178.6 (4)
C2—C1—C6—C5−0.8 (7)N—C7—C8—C9−170.9 (4)
C2—C1—C6—S177.5 (4)S—C7—C8—C910.6 (6)
C4—C5—C6—C10.5 (6)C7—C8—C9—C10−179.9 (4)
N—C5—C6—C1179.6 (4)C8—C9—C10—C10i179.1 (5)
C4—C5—C6—S−178.1 (3)
Symmetry codes: (i) −x+1, −y, −z.
Acknowledgements top

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

references
References top

Chakraborti, A. K., Selvam, C., Kaur, G. & Bhagat, S. (2004). Synlett, pp. 851–855.

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Seijas, J. A., Vazquez, T. M. P., Carballido, R. M. R., Crecente, C. J. & Romar, L. L. (2007). Synlett, pp. 313–317.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, G., Wu, L., Zhuang, L. & Wang, J. (2009). Acta Cryst. E65, o158.