5-Chloro-2-(4-meth­oxy­phen­yl)-1,3-benzo­thia­zole

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

doi:10.1107/S1600536813001955

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o360

doi:10.1107/S1600536813001955

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5-Chloro-2-(4-methoxyphenyl)-1,3-benzothiazole

Sammer Yousuf,^a ^* Shazia Shah,^a Nida Ambreen,^a Khalid M. Khan ^a and Shakil Ahmad ^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 12 January 2013; accepted 19 January 2013; online 9 February 2013)

In the title compound, C₁₄H₁₀ClNOS, the dihedral angle between the benzothiazole ring system and the methoxy-substituted benzene ring is 8.76 (16)°. In the crystal, molecules are stacked in columns along the c axis and no significant intermolecular interactions are observed.

Related literature

For the biological activity of benzothiazole compounds, see: Chohan et al. (2003 ); Khan et al. (2011 ); Hutchinson et al. (2002 ); Burger & Sawhney (1968 ); Palmer et al. (1971 ). For related structures, see: Yousuf et al. (2012a ,b ).

Experimental

Crystal data

C₁₄H₁₀ClNOS
M_r = 275.74
Orthorhombic, P b c n
a = 29.0274 (16) Å
b = 14.5512 (8) Å
c = 5.8686 (3) Å
V = 2478.8 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 273 K
0.37 × 0.22 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.848, T_max = 0.955
13397 measured reflections
2299 independent reflections
1965 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.076
wR(F²) = 0.208
S = 1.15
2299 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.37 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, 1996 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813001955/is5237sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001955/is5237Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813001955/is5237Isup3.cml

checkCIF report

Comment top

Benzothiazole is a well known class of organic compounds with a diverse range of biological activities (Khan et al., 2011; Chohan et al., 2003, Hutchinson et al., 2002; Burger & Sawhney, 1968; Palmer et al., 1971). The title compound is a methoxy phenyl derivative of benzothiazole synthesized as a part of our ongoing project to synthesize bioactive hetereocyclic compounds.

The crystal structure of title compound (Fig. 1), C₁₆H₁₄ClNOS, is similar to that our previously published 5-chloro-2-(3,4,5-trimethoxyphenyl)-1,3-benzothiazole (Yousuf et al., 2012b) with the difference that the 3,4,5-trimethoxyphenyl ring is replaced by the 4-methoxyphenyl phenyl ring. The dihedral angle between planner benzothiazole (S1/N1/C1–C7) and methoxy phenyl rings (C8–C13) is 8.76 (16)°. The bond lengths and angle are similar as in previously published benzothiazole compounds (Yousuf et al., 2012a,b). In the crystal structure the molecules having plane of mirror are arranged in a two-diminesional manner along a and c axes (Fig. 2).

Related literature top

For the biological activity of benzothiazole compounds, see: Chohan et al. (2003); Khan et al. (2011); Hutchinson et al. (2002); Burger & Sawhney (1968); Palmer et al. (1971). For related structures, see: Yousuf et al. (2012a,b).

Experimental top

A mixture of 2-amino-4-cholorobenzenethiol (0.159 g, 1 mmol), 4-methoxybenzaldehyde (0.136 g, 1 mmol), sodium metabisulfite (0.2 g) and N,N-dimethylformamide (10 ml) was refluxed for 2 hrs in a round-bottomed flask. The completion of reaction was monitored by TLC and cool to room temperature followed by addition of cold water to obtain white precipitates. Crystallization from ethanol afforded pure crystal of 5-chloro-2-(4-methoxyphenyl) benzothiazole (yield 0.223 g, 81.1%) found suitable for 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, 1996) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of title compound with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. A crystal packing diagram of the title compound, viewed along the c axis.

5-Chloro-2-(4-methoxyphenyl)-1,3-benzothiazole top

Crystal data top

C₁₄H₁₀ClNOS	F(000) = 1136
M_r = 275.74	D_x = 1.478 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 3307 reflections
a = 29.0274 (16) Å	θ = 2.5–26.3°
b = 14.5512 (8) Å	µ = 0.46 mm⁻¹
c = 5.8686 (3) Å	T = 273 K
V = 2478.8 (2) Å³	Block, colorles
Z = 8	0.37 × 0.22 × 0.10 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2299 independent reflections
Radiation source: fine-focus sealed tube	1965 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scan	θ_max = 25.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −34→34
T_min = 0.848, T_max = 0.955	k = −17→17
13397 measured reflections	l = −6→7

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.208	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0983P)² + 3.3682P] where P = (F_o² + 2F_c²)/3
2299 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₄H₁₀ClNOS	V = 2478.8 (2) Å³
M_r = 275.74	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 29.0274 (16) Å	µ = 0.46 mm⁻¹
b = 14.5512 (8) Å	T = 273 K
c = 5.8686 (3) Å	0.37 × 0.22 × 0.10 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2299 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1965 reflections with I > 2σ(I)
T_min = 0.848, T_max = 0.955	R_int = 0.052
13397 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.076	0 restraints
wR(F²) = 0.208	H-atom parameters constrained
S = 1.15	Δρ_max = 0.63 e Å⁻³
2299 reflections	Δρ_min = −0.37 e Å⁻³
164 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	0.04504 (4)	0.17240 (11)	−0.0360 (2)	0.0787 (5)
S1	0.21904 (4)	0.08514 (7)	0.52664 (16)	0.0494 (4)
O1	0.43838 (11)	0.1057 (2)	0.1916 (6)	0.0656 (9)
N1	0.21907 (12)	0.1613 (2)	0.1301 (5)	0.0437 (8)
C1	0.16642 (15)	0.1048 (2)	0.4009 (6)	0.0450 (9)
C2	0.12234 (17)	0.0857 (3)	0.4807 (7)	0.0502 (10)
H2A	0.1179	0.0592	0.6231	0.060*
C3	0.08560 (16)	0.1072 (3)	0.3433 (7)	0.0556 (11)
H3A	0.0558	0.0946	0.3927	0.067*
C4	0.09246 (15)	0.1475 (3)	0.1304 (8)	0.0530 (10)
C5	0.13595 (15)	0.1688 (3)	0.0488 (7)	0.0471 (9)
H5A	0.1400	0.1968	−0.0922	0.057*
C6	0.17346 (14)	0.1466 (2)	0.1872 (6)	0.0420 (9)
C7	0.24620 (14)	0.1318 (2)	0.2888 (6)	0.0409 (9)
C8	0.29667 (14)	0.1305 (2)	0.2692 (6)	0.0420 (9)
C9	0.32493 (16)	0.0941 (3)	0.4380 (7)	0.0511 (10)
H9A	0.3118	0.0730	0.5727	0.061*
C10	0.37175 (16)	0.0885 (3)	0.4104 (7)	0.0535 (11)
H10A	0.3901	0.0646	0.5261	0.064*
C11	0.39169 (15)	0.1187 (3)	0.2077 (7)	0.0487 (10)
C12	0.36468 (15)	0.1576 (3)	0.0376 (7)	0.0479 (9)
H12A	0.3780	0.1795	−0.0959	0.057*
C13	0.31762 (15)	0.1631 (2)	0.0709 (7)	0.0461 (9)
H13A	0.2994	0.1893	−0.0421	0.055*
C14	0.46063 (17)	0.1316 (4)	−0.0114 (9)	0.0717 (14)
H14A	0.4926	0.1149	−0.0032	0.108*
H14B	0.4580	0.1969	−0.0316	0.108*
H14C	0.4465	0.1007	−0.1379	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0538 (7)	0.1036 (11)	0.0787 (9)	0.0116 (7)	0.0019 (6)	0.0106 (7)
S1	0.0692 (7)	0.0454 (6)	0.0336 (5)	−0.0036 (5)	0.0005 (4)	0.0084 (4)
O1	0.0598 (19)	0.072 (2)	0.065 (2)	0.0054 (15)	−0.0097 (16)	0.0031 (16)
N1	0.058 (2)	0.0384 (16)	0.0347 (16)	−0.0028 (14)	0.0022 (15)	0.0019 (13)
C1	0.069 (3)	0.0347 (18)	0.0308 (18)	−0.0014 (17)	0.0019 (18)	0.0005 (14)
C2	0.068 (3)	0.044 (2)	0.039 (2)	−0.0038 (19)	0.0129 (19)	0.0029 (16)
C3	0.066 (3)	0.051 (2)	0.050 (2)	−0.004 (2)	0.020 (2)	−0.0059 (19)
C4	0.061 (3)	0.046 (2)	0.052 (2)	0.0044 (18)	0.007 (2)	−0.0042 (18)
C5	0.061 (2)	0.0386 (19)	0.042 (2)	0.0006 (17)	0.0043 (19)	−0.0007 (16)
C6	0.061 (2)	0.0313 (16)	0.0334 (18)	−0.0018 (16)	0.0071 (17)	−0.0023 (14)
C7	0.064 (2)	0.0315 (17)	0.0269 (17)	−0.0024 (16)	0.0010 (17)	−0.0002 (14)
C8	0.065 (2)	0.0298 (16)	0.0314 (18)	−0.0007 (15)	−0.0052 (17)	−0.0006 (14)
C9	0.072 (3)	0.045 (2)	0.036 (2)	−0.0032 (19)	−0.0038 (19)	0.0056 (16)
C10	0.071 (3)	0.047 (2)	0.043 (2)	0.0017 (19)	−0.016 (2)	0.0052 (17)
C11	0.056 (2)	0.043 (2)	0.047 (2)	0.0021 (17)	−0.0078 (19)	−0.0040 (17)
C12	0.059 (2)	0.042 (2)	0.043 (2)	−0.0012 (18)	−0.0009 (18)	0.0047 (16)
C13	0.061 (2)	0.0376 (19)	0.040 (2)	0.0003 (17)	−0.0088 (18)	0.0040 (15)
C14	0.055 (3)	0.092 (4)	0.068 (3)	−0.007 (3)	0.001 (2)	0.004 (3)

Geometric parameters (Å, º) top

Cl1—C4	1.726 (5)	C5—H5A	0.9300
S1—C1	1.720 (4)	C7—C8	1.470 (6)
S1—C7	1.741 (4)	C8—C9	1.391 (5)
O1—C11	1.372 (5)	C8—C13	1.396 (5)
O1—C14	1.407 (5)	C9—C10	1.371 (7)
N1—C7	1.293 (5)	C9—H9A	0.9300
N1—C6	1.382 (5)	C10—C11	1.394 (6)
C1—C2	1.391 (6)	C10—H10A	0.9300
C1—C6	1.409 (5)	C11—C12	1.390 (5)
C2—C3	1.373 (7)	C12—C13	1.382 (6)
C2—H2A	0.9300	C12—H12A	0.9300
C3—C4	1.394 (6)	C13—H13A	0.9300
C3—H3A	0.9300	C14—H14A	0.9600
C4—C5	1.386 (6)	C14—H14B	0.9600
C5—C6	1.396 (6)	C14—H14C	0.9600

C1—S1—C7	89.62 (18)	C9—C8—C13	117.8 (4)
C11—O1—C14	118.4 (4)	C9—C8—C7	122.5 (4)
C7—N1—C6	110.9 (3)	C13—C8—C7	119.7 (3)
C2—C1—C6	121.3 (4)	C10—C9—C8	121.5 (4)
C2—C1—S1	129.8 (3)	C10—C9—H9A	119.2
C6—C1—S1	109.0 (3)	C8—C9—H9A	119.2
C3—C2—C1	118.2 (4)	C9—C10—C11	119.6 (4)
C3—C2—H2A	120.9	C9—C10—H10A	120.2
C1—C2—H2A	120.9	C11—C10—H10A	120.2
C2—C3—C4	120.7 (4)	O1—C11—C12	124.4 (4)
C2—C3—H3A	119.6	O1—C11—C10	115.2 (4)
C4—C3—H3A	119.6	C12—C11—C10	120.5 (4)
C5—C4—C3	122.3 (4)	C13—C12—C11	118.7 (4)
C5—C4—Cl1	118.9 (3)	C13—C12—H12A	120.7
C3—C4—Cl1	118.8 (3)	C11—C12—H12A	120.7
C4—C5—C6	117.2 (4)	C12—C13—C8	121.9 (4)
C4—C5—H5A	121.4	C12—C13—H13A	119.0
C6—C5—H5A	121.4	C8—C13—H13A	119.0
N1—C6—C5	124.7 (3)	O1—C14—H14A	109.5
N1—C6—C1	114.9 (4)	O1—C14—H14B	109.5
C5—C6—C1	120.3 (4)	H14A—C14—H14B	109.5
N1—C7—C8	123.7 (3)	O1—C14—H14C	109.5
N1—C7—S1	115.5 (3)	H14A—C14—H14C	109.5
C8—C7—S1	120.6 (3)	H14B—C14—H14C	109.5

C7—S1—C1—C2	179.4 (4)	C1—S1—C7—N1	1.1 (3)
C7—S1—C1—C6	−0.7 (3)	C1—S1—C7—C8	−174.8 (3)
C6—C1—C2—C3	1.2 (6)	N1—C7—C8—C9	−176.7 (3)
S1—C1—C2—C3	−178.9 (3)	S1—C7—C8—C9	−1.1 (5)
C1—C2—C3—C4	−0.4 (6)	N1—C7—C8—C13	0.5 (5)
C2—C3—C4—C5	−0.9 (6)	S1—C7—C8—C13	176.0 (3)
C2—C3—C4—Cl1	179.6 (3)	C13—C8—C9—C10	−1.2 (6)
C3—C4—C5—C6	1.3 (6)	C7—C8—C9—C10	176.0 (4)
Cl1—C4—C5—C6	−179.2 (3)	C8—C9—C10—C11	−0.9 (6)
C7—N1—C6—C5	−178.4 (3)	C14—O1—C11—C12	−1.3 (6)
C7—N1—C6—C1	0.7 (4)	C14—O1—C11—C10	177.8 (4)
C4—C5—C6—N1	178.6 (3)	C9—C10—C11—O1	−176.6 (4)
C4—C5—C6—C1	−0.4 (5)	C9—C10—C11—C12	2.5 (6)
C2—C1—C6—N1	−179.9 (3)	O1—C11—C12—C13	177.1 (4)
S1—C1—C6—N1	0.2 (4)	C10—C11—C12—C13	−1.9 (6)
C2—C1—C6—C5	−0.8 (5)	C11—C12—C13—C8	−0.2 (6)
S1—C1—C6—C5	179.3 (3)	C9—C8—C13—C12	1.8 (5)
C6—N1—C7—C8	174.5 (3)	C7—C8—C13—C12	−175.5 (3)
C6—N1—C7—S1	−1.2 (4)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀ClNOS
M_r	275.74
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	273
a, b, c (Å)	29.0274 (16), 14.5512 (8), 5.8686 (3)
V (Å³)	2478.8 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.37 × 0.22 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.848, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	13397, 2299, 1965
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.076, 0.208, 1.15
No. of reflections	2299
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.37

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1996) and PLATON (Spek, 2009).

Acknowledgements

The authors are thankful to the OPCW, Netherland, and the Higher Education Commission (HEC) Pakistan (project No. 1910) for their financial support.

References

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burger, A. & Sawhney, S. N. (1968). J. Med. Chem. 11, 270–273. CrossRef PubMed Web of Science Google Scholar
Chohan, Z. H., Pervez, H., Scozzafava, A. & Supuran, C. T. (2003). J. Chem. Soc. Pak. 25, 308–313. CAS Google Scholar
Hutchinson, I., Jennings, S. A., Vishnuvajjala, B. R., Wetsell, A. D. & Stevens, M. F. G. (2002). J. Med. Chem. 45, 744–747. Web of Science CrossRef PubMed CAS Google Scholar
Khan, K. M., Rahim, F., Halim, S. A., Taha, M., Khan, M., Perveen, S., Zaheer-ul-Haq, Mesaik, M. A. & Choudhary, M. I., (2011). Bioorg. Med. Chem. 19, 4286–4294. Google Scholar
Nardelli, M. (1996). J. Appl. Cryst. 29, 296–300. CrossRef CAS Web of Science IUCr Journals Google Scholar
Palmer, P. J., Trigg, R. B. & Warrington, J. V. (1971). J. Med. Chem. 14, 248–251. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yousuf, S., Shah, S., Ambreen, N., Khan, K. M. & Ahmad, S. (2012a). Acta Cryst. E68, o2877. CSD CrossRef IUCr Journals Google Scholar
Yousuf, S., Shah, S., Ambreen, N., Khan, K. M. & Ahmad, S. (2012b). Acta Cryst. E68, o3057. CSD CrossRef IUCr Journals Google Scholar