5-Chloro-2-phenyl-1,3-benzothia­zole

Yousuf, S.; Shah, S.; Ambreen, N.; Khan, K.M.; Ahmed, S.

doi:10.1107/S1600536812036057

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2799

doi:10.1107/S1600536812036057

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5-Chloro-2-phenyl-1,3-benzothiazole

Sammer Yousuf,^a ^* Shazia Shah,^a Nida Ambreen,^a Khalid M. Khan ^a and Shakil Ahmed ^a

^aH. E. J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 9 August 2012; accepted 16 August 2012; online 31 August 2012)

In the structure of the title compound, C₁₃H₈ClNS, the dihedral angle between the benzothiazole ring system and the phenyl ring is 7.11 (8)°. In the crystal, molecules are arranged parallel to the c axis.

Related literature

For biological activites of benzothiazole compounds, see: Venkatesh & Pandeya (2009 ); Sreenivasa et al. (2009 ); Kok et al. (2008 ); Siddiqui et al. (2007 ); Maharan et al. (2007 ); Pattan et al. (2005 ); Hout et al. (2004 ); Chohan et al. (2003 ); Bénéteau et al. (1999 ). For the crystal structure of benzothiazole derivatives, see: Lakshmanan et al. (2011 ); Zhang et al. (2008 ).

Experimental

Crystal data

C₁₃H₈ClNS
M_r = 245.71
Monoclinic, P 2₁ /c
a = 7.4057 (9) Å
b = 5.9100 (7) Å
c = 25.165 (3) Å
β = 93.402 (3)°
V = 1099.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 273 K
0.36 × 0.13 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.840, T_max = 0.956
6221 measured reflections
2013 independent reflections
1706 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.093
S = 1.04
2013 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812036057/wn2488sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036057/wn2488Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812036057/wn2488Isup3.cml

checkCIF report

Comment top

Benzothiazoles represent an important class of heterocyclic compounds and are known to have numerous biological activities, including antimicrobial, antimalarial, anticancer, anti-inflamatory, antidiabetic, anticonvulsant, antitumor and anthelmintic properties (Venkatesh & Pandeya, 2009; Sreenivasa et al., 2009; Kok et al., 2008; Siddiqui et al., 2007; Maharan et al., 2007; Pattan et al., 2005; Hout et al., 2004; Chohan et al., 2003; Bénéteau et al., 1999). The title compound was prepared as part of an ongoing research effort to synthesize libraries of hetereocyclic compounds and evaluate thei different biological activities.

In the structure (Fig. 1) of the title compound, C₁₃H₈ClNS, the dihedral angle between the benzothiazole ring system and the phenyl ring is 7.11 (8)°. The bond lengths and angles are similar to those in structurally related benzothiazole compounds (Lakshmanan et al., 2011; Zhang et al., 2008). In the crystal structure the molecules are arranged parallel to the c-axis (Fig. 2).

Related literature top

For biological activites of benzothiazole compounds, see: Venkatesh & Pandeya (2009); Sreenivasa et al. (2009); Kok et al. (2008); Siddiqui et al. (2007); Maharan et al. (2007); Pattan et al. (2005); Hout et al. (2004); Chohan et al. (2003); Bénéteau et al. (1999). For the crystal structure of benzothiazole derivatives, see: Lakshmanan et al. (2011); Zhang et al. (2008).

Experimental top

In a 50 ml round-bottomed flask 2-amino-4-chlorobenzenethiol (0.159 g, 1 mmol), benzaldehyde (0.106 g, 1 mmol), N,N-dimethylformamide (10 ml), and sodium metabisulfite (0.2 g) were added with continuous stirring and allowed to reflux for 2 h. Progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was allowed to cool at room temperature and addition of cold water produced a solid precipitate. Crystallization from ethanol afforded pure crystals of the title compound (0.245 g, 91.8% yield); these were found to be suitable for single-crystal X-ray diffraction studies.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.

Fig. 2. The crystal packing of the title compound.

5-Chloro-2-phenyl-1,3-benzothiazole top

Crystal data top

C₁₃H₈ClNS	F(000) = 504
M_r = 245.71	D_x = 1.484 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4057 (9) Å	Cell parameters from 2167 reflections
b = 5.9100 (7) Å	θ = 3.1–28.2°
c = 25.165 (3) Å	µ = 0.50 mm⁻¹
β = 93.402 (3)°	T = 273 K
V = 1099.5 (2) Å³	Plate, colorless
Z = 4	0.36 × 0.13 × 0.09 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2013 independent reflections
Radiation source: fine-focus sealed tube	1706 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scan	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
T_min = 0.840, T_max = 0.956	k = −7→6
6221 measured reflections	l = −30→30

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0522P)² + 0.1614P] where P = (F_o² + 2F_c²)/3
2013 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₈ClNS	V = 1099.5 (2) Å³
M_r = 245.71	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4057 (9) Å	µ = 0.50 mm⁻¹
b = 5.9100 (7) Å	T = 273 K
c = 25.165 (3) Å	0.36 × 0.13 × 0.09 mm
β = 93.402 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2013 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1706 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.956	R_int = 0.023
6221 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
2013 reflections	Δρ_min = −0.21 e Å⁻³
145 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
Cl1	0.26215 (9)	−0.18042 (11)	0.02881 (2)	0.0660 (2)
S1	0.33963 (7)	0.39652 (8)	0.234075 (19)	0.04489 (18)
N1	0.19011 (19)	−0.0014 (3)	0.22680 (5)	0.0367 (4)
C1	0.2624 (3)	0.3164 (3)	0.35279 (8)	0.0449 (5)
H1B	0.3131	0.4479	0.3399	0.054*
C2	0.2426 (3)	0.2922 (4)	0.40663 (8)	0.0519 (5)
H2A	0.2800	0.4079	0.4298	0.062*
C3	0.1683 (3)	0.0995 (4)	0.42641 (8)	0.0514 (5)
H3A	0.1555	0.0846	0.4628	0.062*
C4	0.1123 (3)	−0.0732 (4)	0.39196 (8)	0.0484 (5)
H4A	0.0617	−0.2040	0.4052	0.058*
C5	0.1315 (2)	−0.0515 (3)	0.33809 (7)	0.0419 (4)
H5A	0.0941	−0.1681	0.3152	0.050*
C6	0.2067 (2)	0.1442 (3)	0.31764 (7)	0.0361 (4)
C7	0.2333 (2)	0.1595 (3)	0.26047 (7)	0.0349 (4)
C9	0.2440 (2)	0.0541 (3)	0.17678 (7)	0.0353 (4)
C10	0.2208 (2)	−0.0858 (3)	0.13211 (7)	0.0395 (4)
H10A	0.1639	−0.2256	0.1340	0.047*
C11	0.2850 (3)	−0.0087 (3)	0.08523 (7)	0.0435 (5)
C12	0.3695 (3)	0.2000 (4)	0.08090 (8)	0.0477 (5)
H12A	0.4101	0.2459	0.0483	0.057*
C13	0.3932 (3)	0.3391 (3)	0.12465 (8)	0.0457 (5)
H13A	0.4498	0.4789	0.1222	0.055*
C14	0.3300 (2)	0.2643 (3)	0.17274 (7)	0.0383 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0921 (5)	0.0674 (4)	0.0395 (3)	−0.0125 (3)	0.0133 (3)	−0.0074 (2)
S1	0.0502 (3)	0.0336 (3)	0.0509 (3)	−0.0091 (2)	0.0039 (2)	−0.0026 (2)
N1	0.0381 (9)	0.0326 (9)	0.0397 (8)	−0.0015 (6)	0.0048 (6)	−0.0006 (6)
C1	0.0482 (12)	0.0366 (11)	0.0496 (11)	−0.0008 (9)	0.0011 (8)	−0.0052 (8)
C2	0.0564 (13)	0.0527 (14)	0.0458 (11)	0.0039 (10)	−0.0028 (9)	−0.0121 (9)
C3	0.0522 (12)	0.0608 (14)	0.0411 (10)	0.0081 (10)	0.0009 (9)	0.0016 (9)
C4	0.0495 (13)	0.0461 (12)	0.0497 (11)	0.0014 (9)	0.0033 (9)	0.0089 (9)
C5	0.0422 (11)	0.0392 (11)	0.0440 (10)	−0.0006 (8)	−0.0007 (8)	−0.0034 (8)
C6	0.0307 (10)	0.0349 (10)	0.0422 (10)	0.0030 (7)	−0.0006 (7)	−0.0025 (7)
C7	0.0282 (9)	0.0308 (10)	0.0453 (10)	0.0003 (7)	−0.0003 (7)	−0.0011 (7)
C9	0.0305 (9)	0.0334 (10)	0.0423 (9)	0.0018 (7)	0.0032 (7)	0.0024 (7)
C10	0.0418 (11)	0.0343 (10)	0.0427 (10)	−0.0029 (8)	0.0041 (8)	0.0000 (8)
C11	0.0456 (12)	0.0464 (12)	0.0388 (10)	0.0020 (9)	0.0045 (8)	0.0000 (8)
C12	0.0472 (12)	0.0511 (13)	0.0457 (11)	0.0002 (9)	0.0102 (8)	0.0110 (9)
C13	0.0435 (11)	0.0398 (11)	0.0545 (11)	−0.0034 (9)	0.0078 (9)	0.0080 (9)
C14	0.0339 (10)	0.0348 (10)	0.0462 (10)	0.0002 (8)	0.0025 (7)	0.0014 (8)

Geometric parameters (Å, º) top

Cl1—C11	1.7453 (19)	C4—H4A	0.9300
S1—C14	1.7279 (18)	C5—C6	1.395 (3)
S1—C7	1.7566 (18)	C5—H5A	0.9300
N1—C7	1.301 (2)	C6—C7	1.466 (2)
N1—C9	1.382 (2)	C9—C10	1.398 (2)
C1—C2	1.379 (3)	C9—C14	1.402 (2)
C1—C6	1.395 (3)	C10—C11	1.376 (2)
C1—H1B	0.9300	C10—H10A	0.9300
C2—C3	1.371 (3)	C11—C12	1.390 (3)
C2—H2A	0.9300	C12—C13	1.377 (3)
C3—C4	1.386 (3)	C12—H12A	0.9300
C3—H3A	0.9300	C13—C14	1.395 (3)
C4—C5	1.377 (3)	C13—H13A	0.9300

C14—S1—C7	88.93 (8)	N1—C7—S1	115.77 (13)
C7—N1—C9	110.29 (15)	C6—C7—S1	120.63 (13)
C2—C1—C6	120.18 (19)	N1—C9—C10	124.31 (16)
C2—C1—H1B	119.9	N1—C9—C14	115.66 (15)
C6—C1—H1B	119.9	C10—C9—C14	120.02 (15)
C3—C2—C1	120.75 (19)	C11—C10—C9	117.48 (18)
C3—C2—H2A	119.6	C11—C10—H10A	121.3
C1—C2—H2A	119.6	C9—C10—H10A	121.3
C2—C3—C4	119.73 (18)	C10—C11—C12	122.76 (17)
C2—C3—H3A	120.1	C10—C11—Cl1	118.90 (15)
C4—C3—H3A	120.1	C12—C11—Cl1	118.33 (14)
C5—C4—C3	120.16 (19)	C13—C12—C11	120.25 (17)
C5—C4—H4A	119.9	C13—C12—H12A	119.9
C3—C4—H4A	119.9	C11—C12—H12A	119.9
C4—C5—C6	120.47 (18)	C12—C13—C14	118.07 (18)
C4—C5—H5A	119.8	C12—C13—H13A	121.0
C6—C5—H5A	119.8	C14—C13—H13A	121.0
C1—C6—C5	118.72 (17)	C13—C14—C9	121.40 (17)
C1—C6—C7	121.69 (17)	C13—C14—S1	129.28 (15)
C5—C6—C7	119.52 (15)	C9—C14—S1	109.32 (12)
N1—C7—C6	123.50 (16)

C6—C1—C2—C3	0.1 (3)	C7—N1—C9—C14	−0.3 (2)
C1—C2—C3—C4	0.0 (3)	N1—C9—C10—C11	−178.70 (17)
C2—C3—C4—C5	0.1 (3)	C14—C9—C10—C11	0.1 (3)
C3—C4—C5—C6	−0.2 (3)	C9—C10—C11—C12	−0.4 (3)
C2—C1—C6—C5	−0.1 (3)	C9—C10—C11—Cl1	178.89 (14)
C2—C1—C6—C7	−177.15 (17)	C10—C11—C12—C13	0.5 (3)
C4—C5—C6—C1	0.2 (3)	Cl1—C11—C12—C13	−178.86 (15)
C4—C5—C6—C7	177.29 (16)	C11—C12—C13—C14	−0.2 (3)
C9—N1—C7—C6	−175.21 (15)	C12—C13—C14—C9	−0.2 (3)
C9—N1—C7—S1	1.28 (19)	C12—C13—C14—S1	179.72 (15)
C1—C6—C7—N1	177.03 (17)	N1—C9—C14—C13	179.11 (17)
C5—C6—C7—N1	0.0 (3)	C10—C9—C14—C13	0.2 (3)
C1—C6—C7—S1	0.7 (2)	N1—C9—C14—S1	−0.8 (2)
C5—C6—C7—S1	−176.27 (14)	C10—C9—C14—S1	−179.71 (14)
C14—S1—C7—N1	−1.50 (15)	C7—S1—C14—C13	−178.71 (18)
C14—S1—C7—C6	175.10 (14)	C7—S1—C14—C9	1.20 (14)
C7—N1—C9—C10	178.56 (17)

Experimental details

Crystal data
Chemical formula	C₁₃H₈ClNS
M_r	245.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	7.4057 (9), 5.9100 (7), 25.165 (3)
β (°)	93.402 (3)
V (Å³)	1099.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.36 × 0.13 × 0.09

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.840, 0.956
No. of measured, independent and observed [I > 2σ(I)] reflections	6221, 2013, 1706
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 1.04
No. of reflections	2013
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Acknowledgements

The authors thank OPCW, The Netherlands, and the Higher Education Commission, Pakistan (project No. 1910), for their financial support.

References

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