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

Abstract

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,

• a = 26.1607 (2) Å

• b = 4.0565 (2) Å

• c = 12.1435 (3) Å

• β = 91.5720 (1)°

• V = 1288.19 (7) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms attached to C and O atoms were placed in geometrically idealized positions with Csp²—H = 0.93 Å and O—H = 0.82 Å. The isotropic displacement parameters for H atoms were fixed as U_iso(H) = 1.2U_eq(carrier C atom) and U_iso(H1) = 1.5U_eq(O1).

Figures

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.

Crystal data

C14H9BrN2OS	Z = 4
Mr = 333.20	F(000) = 664
Monoclinic, P21/c	Dx = 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

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

Refinement

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(Fo2)] where P = (Fo2 + 2Fc2)/3
2232 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.54 e Å−3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x, −y+5/2, z+1/2.