2-[(1,3-Benzothia­zol-2-yl)imino­meth­yl]-4-bromo­phenol

Diao, H.-P.; Sun, T.-J.; Liu, W.

doi:10.1107/S160053681101275X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1096

doi:10.1107/S160053681101275X

Open

access

2-[(1,3-Benzothiazol-2-yl)iminomethyl]-4-bromophenol

Hai-Peng Diao,^a Ti-Jian Sun ^a and Wen Liu ^a ^*

^aDepartment of Chemistry, Shanxi Medical University, Taiyuan, Shanxi 030001, People's Republic of China
^*Correspondence e-mail: liuwen0616@163.com

(Received 5 March 2011; accepted 6 April 2011; online 13 April 2011)

In the title compound, C₁₄H₉BrN₂OS, the dihedral angle between the benzene rings is 3.1 (3)°. An intramolecular O—H⋯N(imine) hydrogen bond occurs. The crystal structure is stabilized by weak intermolecular C—H⋯O interactions.

Related literature

For the uses of Schiff bases, see: Da Silva et al. (2011 ); Dhar & Taploo (1982 ); Przybylski et al. (2009 ); Guo et al. (2007 ); Bringmann et al. (2004 ). For the structures of closely related imines, see: Liu et al. (2009 ); Asiri et al. (2010 ).

Experimental

Crystal data

C₁₄H₉BrN₂OS
M_r = 333.20
Monoclinic, P 2₁ /c
a = 26.1607 (2) Å
b = 4.0565 (2) Å
c = 12.1435 (3) Å
β = 91.5720 (1)°
V = 1288.19 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.34 mm⁻¹
T = 296 K
0.45 × 0.40 × 0.38 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.242, T_max = 0.281
11848 measured reflections
2232 independent reflections
1466 reflections with I > 2σ(I)
R_int = 0.138

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.118
S = 0.93
2232 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.87	2.600 (6)	148
C7—H7⋯O1ⁱ	0.93	2.47	3.345 (6)	157
Symmetry code: (i) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101275X/bh2345sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101275X/bh2345Isup2.hkl

checkCIF report

Comment top

Schiff bases are some of the most widely used organic compounds. They are used as pigments and dyes, catalysts, intermediates in organic synthesis, and as polymer stabilisers (Da Silva et al., 2011). They have also been shown to exhibit a broad range of biological activities, including antifungal, antibacterial, antimalarial, antiproliferative, anti-inflammatory, antiviral, and antipyretic properties (Dhar & Taploo, 1982; Przybylski et al., 2009). The imine group present in such compounds has been shown to be critical to their biological activities (Guo et al., 2007; Bringmann et al., 2004). It was thus of interest to synthesize the title compound.

The X-ray structural analysis confirmed the assignment of the structure of the title compound (Fig. 1). The bond length of C8—N1 is 1.396 (6) Å, which is shorter than normal C—N [1.47 Å]. The dihedral angle between the two benzene rings (C1···C6 and C9···C14) is 3.1 (3)°, it is a little larger than 2.81 (9)° or 2.6 (1)° found in a related structure (Liu et al., 2009; Asiri et al., 2010). In the crystal structure (Fig. 2), the compound is further stabilized by intramolecular O—H···N and weak intermolecular C—H···O hydrogen-bond interactions.

Related literature top

For the uses of Schiff bases, see: Da Silva et al. (2011); Dhar & Taploo (1982); Przybylski et al. (2009); Guo et al. (2007); Bringmann et al. (2004). For the structures of closely related imines, see: Liu et al. (2009); Asiri et al. (2010).

Experimental top

10 mL of 5 mmol 5-bromo-2-hydroxybenzaldehyde ethanol solution was added to 10 mL of the 5 mmol (0.7515 g) of 2-aminobenzothiazole ethanol solution. The resulting solution was refluxed for about 3 h, and then cooled to room temperature. Yellow crystals of title compound were obtained after 2 weeks of slow evaporation of the filtrate at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

2-[(1,3-Benzothiazol-2-yl)iminomethyl]-4-bromophenol top

Crystal data top

C₁₄H₉BrN₂OS	Z = 4
M_r = 333.20	F(000) = 664
Monoclinic, P2₁/c	D_x = 1.718 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 26.1607 (2) Å	θ = 3.4–21.4°
b = 4.0565 (2) Å	µ = 3.34 mm⁻¹
c = 12.1435 (3) Å	T = 296 K
β = 91.5720 (1)°	Block, yellow
V = 1288.19 (7) Å³	0.45 × 0.40 × 0.38 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2232 independent reflections
Radiation source: fine-focus sealed tube	1466 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.138
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −30→30
T_min = 0.242, T_max = 0.281	k = −4→4
11848 measured reflections	l = −14→14

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
2232 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³
0 constraints

Crystal data top

C₁₄H₉BrN₂OS	V = 1288.19 (7) Å³
M_r = 333.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 26.1607 (2) Å	µ = 3.34 mm⁻¹
b = 4.0565 (2) Å	T = 296 K
c = 12.1435 (3) Å	0.45 × 0.40 × 0.38 mm
β = 91.5720 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2232 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1466 reflections with I > 2σ(I)
T_min = 0.242, T_max = 0.281	R_int = 0.138
11848 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.93	Δρ_max = 0.36 e Å⁻³
2232 reflections	Δρ_min = −0.54 e Å⁻³
173 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.03658 (2)	1.69312 (15)	0.65038 (5)	0.0536 (2)
S2	0.29866 (5)	0.7609 (3)	0.70906 (12)	0.0488 (4)
C1	0.17288 (19)	1.3148 (12)	0.5361 (4)	0.0370 (11)
O1	0.20795 (15)	1.3280 (10)	0.3543 (3)	0.0582 (10)
H1	0.2300	1.2208	0.3877	0.087*
C12	0.4377 (2)	0.3239 (15)	0.7216 (6)	0.0633 (17)
H12	0.4606	0.2193	0.7700	0.076*
C4	0.0898 (2)	1.6691 (13)	0.4506 (4)	0.0458 (13)
H4	0.0620	1.7888	0.4225	0.055*
C6	0.13249 (18)	1.4049 (11)	0.6017 (4)	0.0372 (12)
H6	0.1335	1.3473	0.6758	0.045*
N2	0.33356 (16)	0.7896 (11)	0.5088 (4)	0.0471 (11)
N1	0.25338 (15)	1.0410 (11)	0.5215 (3)	0.0432 (10)
C2	0.17096 (19)	1.4091 (12)	0.4229 (4)	0.0399 (12)
C8	0.29517 (19)	0.8711 (13)	0.5676 (4)	0.0437 (13)
C5	0.09127 (19)	1.5761 (12)	0.5601 (4)	0.0381 (12)
C7	0.21554 (18)	1.1329 (12)	0.5801 (4)	0.0386 (12)
H7	0.2160	1.0782	0.6545	0.046*
C9	0.3704 (2)	0.6300 (13)	0.5745 (5)	0.0469 (14)
C3	0.1294 (2)	1.5847 (13)	0.3824 (4)	0.0501 (14)
H3	0.1279	1.6472	0.3087	0.060*
C11	0.3918 (2)	0.4411 (14)	0.7602 (5)	0.0596 (16)
H11	0.3837	0.4206	0.8340	0.071*
C10	0.35821 (19)	0.5906 (12)	0.6847 (4)	0.0432 (13)
C13	0.4499 (2)	0.3597 (14)	0.6131 (6)	0.0653 (18)
H13	0.4812	0.2816	0.5897	0.078*
C14	0.4168 (2)	0.5088 (15)	0.5376 (5)	0.0581 (16)
H14	0.4253	0.5279	0.4640	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0431 (3)	0.0658 (4)	0.0521 (4)	0.0039 (3)	0.0053 (2)	−0.0054 (3)
S2	0.0435 (8)	0.0614 (9)	0.0415 (8)	0.0046 (6)	0.0040 (6)	0.0028 (7)
C1	0.046 (3)	0.041 (3)	0.023 (3)	−0.001 (2)	−0.005 (2)	−0.003 (2)
O1	0.058 (2)	0.089 (3)	0.0284 (19)	0.013 (2)	0.0052 (18)	0.008 (2)
C12	0.046 (4)	0.064 (4)	0.080 (5)	0.001 (3)	−0.003 (3)	0.010 (4)
C4	0.043 (3)	0.050 (3)	0.044 (3)	−0.001 (3)	−0.010 (3)	−0.001 (3)
C6	0.042 (3)	0.045 (3)	0.025 (3)	−0.006 (2)	0.001 (2)	−0.004 (2)
N2	0.043 (3)	0.060 (3)	0.039 (3)	−0.004 (2)	0.002 (2)	−0.005 (2)
N1	0.040 (2)	0.054 (3)	0.036 (2)	−0.006 (2)	0.001 (2)	−0.004 (2)
C2	0.043 (3)	0.050 (3)	0.027 (3)	−0.007 (2)	0.001 (2)	−0.003 (2)
C8	0.039 (3)	0.054 (3)	0.038 (3)	−0.005 (3)	0.005 (2)	−0.004 (3)
C5	0.042 (3)	0.038 (3)	0.034 (3)	−0.003 (2)	−0.003 (2)	−0.002 (2)
C7	0.044 (3)	0.050 (3)	0.021 (3)	−0.008 (2)	−0.003 (2)	0.002 (2)
C9	0.039 (3)	0.050 (3)	0.052 (3)	−0.008 (3)	0.003 (3)	−0.004 (3)
C3	0.056 (4)	0.067 (4)	0.027 (3)	0.003 (3)	−0.007 (3)	0.005 (3)
C11	0.054 (4)	0.065 (4)	0.060 (4)	−0.001 (3)	−0.003 (3)	0.004 (3)
C10	0.036 (3)	0.043 (3)	0.051 (3)	−0.006 (2)	0.002 (3)	−0.002 (3)
C13	0.042 (3)	0.060 (4)	0.094 (5)	0.002 (3)	0.006 (4)	−0.012 (4)
C14	0.051 (4)	0.065 (4)	0.059 (4)	−0.008 (3)	0.012 (3)	−0.011 (3)

Geometric parameters (Å, º) top

Br1—C5	1.887 (5)	C6—H6	0.9300
S2—C10	1.737 (5)	N2—C8	1.291 (6)
S2—C8	1.775 (5)	N2—C9	1.393 (7)
C1—C6	1.390 (6)	N1—C7	1.290 (6)
C1—C2	1.426 (6)	N1—C8	1.396 (6)
C1—C7	1.430 (7)	C2—C3	1.380 (7)
O1—C2	1.335 (5)	C7—H7	0.9300
O1—H1	0.8200	C9—C10	1.393 (7)
C12—C13	1.372 (9)	C9—C14	1.395 (7)
C12—C11	1.384 (8)	C3—H3	0.9300
C12—H12	0.9300	C11—C10	1.392 (7)
C4—C5	1.382 (7)	C11—H11	0.9300
C4—C3	1.387 (7)	C13—C14	1.382 (8)
C4—H4	0.9300	C13—H13	0.9300
C6—C5	1.367 (6)	C14—H14	0.9300

C10—S2—C8	87.6 (2)	C6—C5—Br1	121.1 (4)
C6—C1—C2	118.3 (5)	C4—C5—Br1	119.2 (4)
C6—C1—C7	121.3 (4)	N1—C7—C1	123.1 (4)
C2—C1—C7	120.4 (4)	N1—C7—H7	118.5
C2—O1—H1	109.5	C1—C7—H7	118.5
C13—C12—C11	121.0 (6)	C10—C9—N2	115.5 (5)
C13—C12—H12	119.5	C10—C9—C14	119.5 (6)
C11—C12—H12	119.5	N2—C9—C14	125.0 (5)
C5—C4—C3	120.3 (5)	C2—C3—C4	120.6 (5)
C5—C4—H4	119.8	C2—C3—H3	119.7
C3—C4—H4	119.8	C4—C3—H3	119.7
C5—C6—C1	121.8 (5)	C12—C11—C10	117.7 (6)
C5—C6—H6	119.1	C12—C11—H11	121.2
C1—C6—H6	119.1	C10—C11—H11	121.2
C8—N2—C9	109.8 (4)	C11—C10—C9	121.7 (5)
C7—N1—C8	121.7 (4)	C11—C10—S2	127.9 (4)
O1—C2—C3	118.9 (4)	C9—C10—S2	110.4 (4)
O1—C2—C1	121.9 (5)	C12—C13—C14	121.7 (6)
C3—C2—C1	119.2 (5)	C12—C13—H13	119.1
N2—C8—N1	121.2 (5)	C14—C13—H13	119.1
N2—C8—S2	116.7 (4)	C13—C14—C9	118.4 (6)
N1—C8—S2	122.1 (4)	C13—C14—H14	120.8
C6—C5—C4	119.7 (5)	C9—C14—H14	120.8

C2—C1—C6—C5	0.8 (7)	C8—N2—C9—C10	0.7 (6)
C7—C1—C6—C5	−179.3 (4)	C8—N2—C9—C14	−180.0 (5)
C6—C1—C2—O1	−179.1 (5)	O1—C2—C3—C4	178.9 (5)
C7—C1—C2—O1	1.1 (7)	C1—C2—C3—C4	0.0 (7)
C6—C1—C2—C3	−0.1 (7)	C5—C4—C3—C2	−0.4 (8)
C7—C1—C2—C3	−180.0 (5)	C13—C12—C11—C10	1.2 (9)
C9—N2—C8—N1	178.7 (4)	C12—C11—C10—C9	−1.6 (8)
C9—N2—C8—S2	−0.6 (6)	C12—C11—C10—S2	−179.6 (4)
C7—N1—C8—N2	−177.8 (5)	N2—C9—C10—C11	−178.8 (5)
C7—N1—C8—S2	1.5 (7)	C14—C9—C10—C11	1.8 (8)
C10—S2—C8—N2	0.3 (4)	N2—C9—C10—S2	−0.4 (6)
C10—S2—C8—N1	−179.0 (4)	C14—C9—C10—S2	−179.8 (4)
C1—C6—C5—C4	−1.3 (7)	C8—S2—C10—C11	178.3 (5)
C1—C6—C5—Br1	179.5 (4)	C8—S2—C10—C9	0.1 (4)
C3—C4—C5—C6	1.1 (7)	C11—C12—C13—C14	−1.0 (9)
C3—C4—C5—Br1	−179.7 (4)	C12—C13—C14—C9	1.2 (9)
C8—N1—C7—C1	178.3 (4)	C10—C9—C14—C13	−1.5 (8)
C6—C1—C7—N1	179.0 (4)	N2—C9—C14—C13	179.1 (5)
C2—C1—C7—N1	−1.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.600 (6)	148
C7—H7···O1ⁱ	0.93	2.47	3.345 (6)	157

Symmetry code: (i) x, −y+5/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉BrN₂OS
M_r	333.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	26.1607 (2), 4.0565 (2), 12.1435 (3)
β (°)	91.5720 (1)
V (Å³)	1288.19 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.34
Crystal size (mm)	0.45 × 0.40 × 0.38

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.242, 0.281
No. of measured, independent and observed [I > 2σ(I)] reflections	11848, 2232, 1466
R_int	0.138
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.118, 0.93
No. of reflections	2232
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.54

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.600 (6)	148
C7—H7···O1ⁱ	0.93	2.47	3.345 (6)	157

Symmetry code: (i) x, −y+5/2, z+1/2.

Acknowledgements

We acknowledge financial support from the Youth Foundation of Shanxi Medical University in China (grant No. 02200922).

References

Asiri, A. M., Khan, S. A., Tan, K. W. & Ng, S. W. (2010). Acta Cryst. E66, o1826. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bringmann, G., Dreyer, M., Faber, J. H., Dalsgaard, P. W., Staerk, D., Jaroszewski, J. W., Ndangalasi, H., Mbago, F., Brun, R. & Søren Brøgger, C. (2004). J. Nat. Prod. 67, 743–748. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Da Silva, C. M., Da Silva, D. L., Modolo, L. V., Alves, R. B., De Resende, M. A., Martins, C. V. B. & De Fátima, Â. (2011). J. Adv. Res. 2, 1–8. CrossRef Google Scholar
Dhar, D. N. & Taploo, C. L. (1982). J. Sci. Ind. Res. 41, 501–506. CAS Google Scholar
Guo, Z., Xing, R., Liu, S., Zhong, Z., Ji, X., Wang, L. & Li, P. (2007). Carbohydr. Res. 342, 1329–1332. Web of Science CrossRef PubMed CAS Google Scholar
Liu, S.-Q., Bi, C.-F., Chen, L.-Y. & Fan, Y.-H. (2009). Acta Cryst. E65, o738. Web of Science CSD CrossRef IUCr Journals Google Scholar
Przybylski, P., Huczynski, A., Pyta, K., Brzezinski, B. & Bartl, F. (2009). Curr. Org. Chem. 13, 124–148. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar