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

Liu, S.-Q.; Bi, C.-F.; Chen, L.-Y.; Fan, Y.-H.

doi:10.1107/S1600536809007934

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o738

doi:10.1107/S1600536809007934

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

Si-Quan Liu,^a ^* Cai-Feng Bi,^a Liang-Yu Chen ^b and Yu-Hua Fan ^a

^aSchool of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266012, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, People's Republic of China
^*Correspondence e-mail: chm_liusq@ujn.cn

(Received 4 February 2009; accepted 4 March 2009; online 11 March 2009)

The title compound, C₁₄H₁₀N₂OS, is nearly planar, with a maximum deviation of 0.0698 (13) Å from the mean plane, and exists in an E configuration with respect to the C=N bond. The dihedral angle between the two benzene rings is 2.81 (9)°. There is an intramolecular O—H⋯N hydrogen bond and intermolecular C—H⋯O and C—H⋯N hydrogen bonds.

Related literature

For related structures of 2-aminobenzothiazole derivatives and their Schiff bases, see: Büyükgüngör et al. (2004 ); Liang et al. (1999 ); Liu et al. (2009 ). For the biological activity of the title compound and related structures, see: Yan et al. (1999 ).

Experimental

Crystal data

C₁₄H₁₀N₂OS
M_r = 254.30
Orthorhombic, P b c a
a = 12.150 (2) Å
b = 8.9578 (15) Å
c = 22.026 (4) Å
V = 2397.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.51 × 0.15 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
12166 measured reflections
2353 independent reflections
1939 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.113
S = 1.06
2353 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.82	1.88	2.6034 (19)	147
C7—H7⋯O1ⁱ	0.93	2.43	3.309 (2)	158
C2—H2⋯N1ⁱⁱ	0.93	2.68	3.593 (2)	167
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809007934/is2387sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007934/is2387Isup2.hkl

checkCIF report

Comment top

A wide range of biological activities have been attributed to the title compounds and compound having similar structure (Yan et al., 1999). One kind of schiff base of 2-aminobenzothiazole was prepared by Büyükgüngör et al. (2004). The title compound has been prepared to utilize it as an intermediate ligand and for complexation with various metals (Liang et al., 1999; Liu et al., 2009).

In the molecule of the title compound (Fig. 1), the bond length of C8—N2 [1.379 (2) Å] is shorter than normal C—N (1.47 Å). The entire molecule is almost planar due to the C6—C7—N2—C8—N1—C9 π-π conjunction. The dihedral angle between the two benzene rings (C1—C6 and C9—C14) is 2.81 (9)°. The benzothiazol and the o-hydroxy benzenyl at the C=N double bond are in an E configuration due to the hydrogen bond between O—H···N.

In the crystal structure, intermolecular C—H···O and C—H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related structures of 2-aminobenzothiazole derivatives and their Schiff bases, see: Büyükgüngör et al. (2004); Liang et al. (1999); Liu et al. (2009). For the biological activity of the title compound and related structures, see: Yan et al. (1999).

Experimental top

2-Aminobenzithiazole (0.01 mol) and salicylaldehyde (0.01 mol) were dissolved in 50 ml ethanol at 298 K, then the reaction temperature raised to 343 K. After 3 h of reaction, the reaction mixture was condensed to 20 ml and cooled down to 273 K to give a dark orange solid. The crude was purified by column chromatography, affording salmon pink crystals of the title compound (yield 91%; m.p. 417–418 K).

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).

Figures top

	Fig. 1. Molecular structure of the title compound, with 30% probability displacement ellipsoids.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds were shown by dashed lines.

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

Crystal data top

C₁₄H₁₀N₂OS	D_x = 1.409 Mg m⁻³
M_r = 254.30	Melting point: 417 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3147 reflections
a = 12.150 (2) Å	θ = 2.5–27.1°
b = 8.9578 (15) Å	µ = 0.26 mm⁻¹
c = 22.026 (4) Å	T = 298 K
V = 2397.4 (7) Å³	Rod, yellow
Z = 8	0.51 × 0.15 × 0.11 mm
F(000) = 1056

Data collection top

Bruker SMART APEX diffractometer	1939 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 26.0°, θ_min = 1.9°
ϕ and ω scans	h = −14→14
12166 measured reflections	k = −11→10
2353 independent reflections	l = −27→18

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) = 0.113	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0596P)² + 0.4758P] where P = (F_o² + 2F_c²)/3
2353 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₄H₁₀N₂OS	V = 2397.4 (7) Å³
M_r = 254.30	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.150 (2) Å	µ = 0.26 mm⁻¹
b = 8.9578 (15) Å	T = 298 K
c = 22.026 (4) Å	0.51 × 0.15 × 0.11 mm

Data collection top

Bruker SMART APEX diffractometer	1939 reflections with I > 2σ(I)
12166 measured reflections	R_int = 0.036
2353 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	Δρ_max = 0.26 e Å⁻³
2353 reflections	Δρ_min = −0.24 e Å⁻³
163 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
C1	0.88027 (14)	0.3483 (2)	0.21383 (9)	0.0409 (4)
C2	0.91856 (18)	0.4419 (2)	0.16848 (10)	0.0541 (6)
H2	0.9937	0.4497	0.1611	0.065*
C3	0.8451 (2)	0.5230 (3)	0.13448 (10)	0.0570 (6)
H3	0.8715	0.5858	0.1042	0.068*
C4	0.73328 (19)	0.5138 (2)	0.14422 (9)	0.0530 (5)
H4	0.6847	0.5691	0.1206	0.064*
C5	0.69463 (16)	0.4221 (2)	0.18923 (9)	0.0451 (5)
H5	0.6192	0.4159	0.1960	0.054*
C6	0.76636 (14)	0.3374 (2)	0.22515 (8)	0.0370 (4)
C7	0.72317 (13)	0.2428 (2)	0.27182 (8)	0.0381 (4)
H7	0.6474	0.2382	0.2773	0.046*
C8	0.74236 (14)	0.0726 (2)	0.35054 (8)	0.0366 (4)
C9	0.74360 (15)	−0.0870 (2)	0.42653 (8)	0.0397 (4)
C10	0.78616 (17)	−0.1805 (2)	0.47105 (9)	0.0519 (5)
H10	0.8619	−0.1912	0.4753	0.062*
C11	0.71662 (19)	−0.2563 (3)	0.50844 (10)	0.0574 (6)
H11	0.7452	−0.3190	0.5382	0.069*
C12	0.60333 (19)	−0.2410 (3)	0.50247 (11)	0.0614 (6)
H12	0.5570	−0.2935	0.5284	0.074*
C13	0.55866 (18)	−0.1495 (3)	0.45897 (10)	0.0589 (6)
H13	0.4828	−0.1395	0.4551	0.071*
C14	0.62954 (15)	−0.0724 (2)	0.42097 (9)	0.0419 (4)
N1	0.80522 (12)	−0.00477 (18)	0.38564 (7)	0.0419 (4)
N2	0.78539 (11)	0.16428 (17)	0.30618 (7)	0.0382 (4)
O1	0.95340 (10)	0.26804 (18)	0.24619 (7)	0.0549 (4)
H1	0.9210	0.2214	0.2728	0.082*
S1	0.59914 (4)	0.05133 (6)	0.36285 (2)	0.04566 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0337 (9)	0.0443 (11)	0.0447 (10)	−0.0016 (8)	0.0039 (8)	−0.0077 (8)
C2	0.0457 (11)	0.0596 (14)	0.0571 (13)	−0.0105 (10)	0.0130 (10)	−0.0046 (10)
C3	0.0714 (16)	0.0517 (13)	0.0480 (12)	−0.0107 (12)	0.0098 (11)	0.0030 (10)
C4	0.0639 (14)	0.0503 (12)	0.0449 (12)	0.0039 (11)	−0.0043 (10)	0.0009 (9)
C5	0.0394 (10)	0.0477 (12)	0.0481 (11)	0.0018 (9)	−0.0018 (8)	−0.0045 (9)
C6	0.0320 (9)	0.0384 (10)	0.0405 (10)	−0.0008 (7)	0.0018 (7)	−0.0081 (8)
C7	0.0261 (8)	0.0428 (10)	0.0455 (10)	−0.0003 (8)	0.0018 (7)	−0.0058 (8)
C8	0.0277 (9)	0.0405 (10)	0.0416 (10)	0.0008 (7)	0.0012 (7)	−0.0073 (8)
C9	0.0390 (10)	0.0424 (11)	0.0378 (10)	0.0018 (8)	0.0022 (8)	−0.0064 (8)
C10	0.0478 (11)	0.0582 (13)	0.0497 (12)	0.0082 (10)	−0.0029 (9)	0.0003 (10)
C11	0.0681 (14)	0.0566 (14)	0.0475 (12)	0.0035 (11)	−0.0003 (10)	0.0086 (10)
C12	0.0591 (14)	0.0670 (15)	0.0579 (14)	−0.0063 (12)	0.0101 (10)	0.0144 (12)
C13	0.0427 (11)	0.0685 (15)	0.0656 (14)	−0.0061 (10)	0.0086 (10)	0.0116 (12)
C14	0.0384 (9)	0.0430 (11)	0.0443 (11)	−0.0005 (8)	0.0002 (8)	−0.0022 (8)
N1	0.0332 (8)	0.0472 (9)	0.0453 (9)	0.0050 (7)	0.0017 (7)	−0.0014 (8)
N2	0.0302 (7)	0.0420 (9)	0.0425 (8)	0.0007 (6)	0.0034 (6)	−0.0034 (7)
O1	0.0289 (6)	0.0699 (10)	0.0660 (10)	0.0016 (7)	0.0052 (6)	0.0088 (8)
S1	0.0277 (3)	0.0558 (4)	0.0535 (3)	−0.0020 (2)	−0.00019 (19)	0.0079 (2)

Geometric parameters (Å, º) top

C1—O1	1.347 (2)	C8—N2	1.379 (2)
C1—C2	1.384 (3)	C8—S1	1.7714 (18)
C1—C6	1.410 (2)	C9—N1	1.384 (2)
C2—C3	1.373 (3)	C9—C10	1.389 (3)
C2—H2	0.9300	C9—C14	1.397 (3)
C3—C4	1.378 (3)	C10—C11	1.362 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.371 (3)	C11—C12	1.390 (3)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.400 (3)	C12—C13	1.373 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—C7	1.432 (3)	C13—C14	1.385 (3)
C7—N2	1.280 (2)	C13—H13	0.9300
C7—H7	0.9300	C14—S1	1.733 (2)
C8—N1	1.289 (2)	O1—H1	0.8200

O1—C1—C2	118.89 (16)	N2—C8—S1	123.03 (13)
O1—C1—C6	121.15 (17)	N1—C9—C10	125.37 (17)
C2—C1—C6	119.96 (18)	N1—C9—C14	115.45 (16)
C3—C2—C1	119.71 (19)	C10—C9—C14	119.17 (18)
C3—C2—H2	120.1	C11—C10—C9	119.79 (19)
C1—C2—H2	120.1	C11—C10—H10	120.1
C2—C3—C4	121.6 (2)	C9—C10—H10	120.1
C2—C3—H3	119.2	C10—C11—C12	120.5 (2)
C4—C3—H3	119.2	C10—C11—H11	119.7
C5—C4—C3	119.1 (2)	C12—C11—H11	119.7
C5—C4—H4	120.4	C13—C12—C11	121.1 (2)
C3—C4—H4	120.4	C13—C12—H12	119.4
C4—C5—C6	121.34 (19)	C11—C12—H12	119.4
C4—C5—H5	119.3	C12—C13—C14	118.3 (2)
C6—C5—H5	119.3	C12—C13—H13	120.9
C5—C6—C1	118.29 (17)	C14—C13—H13	120.9
C5—C6—C7	119.87 (16)	C13—C14—C9	121.12 (18)
C1—C6—C7	121.84 (17)	C13—C14—S1	129.24 (16)
N2—C7—C6	122.23 (15)	C9—C14—S1	109.64 (14)
N2—C7—H7	118.9	C8—N1—C9	110.86 (15)
C6—C7—H7	118.9	C7—N2—C8	121.47 (15)
N1—C8—N2	121.36 (16)	C1—O1—H1	109.5
N1—C8—S1	115.61 (14)	C14—S1—C8	88.44 (9)

O1—C1—C2—C3	179.13 (19)	C12—C13—C14—C9	0.1 (3)
C6—C1—C2—C3	−0.4 (3)	C12—C13—C14—S1	−179.36 (17)
C1—C2—C3—C4	−0.1 (3)	N1—C9—C14—C13	179.63 (19)
C2—C3—C4—C5	0.5 (3)	C10—C9—C14—C13	−0.1 (3)
C3—C4—C5—C6	−0.3 (3)	N1—C9—C14—S1	−0.8 (2)
C4—C5—C6—C1	−0.2 (3)	C10—C9—C14—S1	179.44 (15)
C4—C5—C6—C7	179.96 (18)	N2—C8—N1—C9	179.65 (15)
O1—C1—C6—C5	−178.96 (17)	S1—C8—N1—C9	−1.0 (2)
C2—C1—C6—C5	0.5 (3)	C10—C9—N1—C8	−179.13 (18)
O1—C1—C6—C7	0.9 (3)	C14—C9—N1—C8	1.2 (2)
C2—C1—C6—C7	−179.64 (18)	C6—C7—N2—C8	−179.39 (16)
C5—C6—C7—N2	−179.38 (17)	N1—C8—N2—C7	−179.05 (17)
C1—C6—C7—N2	0.8 (3)	S1—C8—N2—C7	1.6 (2)
N1—C9—C10—C11	−179.61 (19)	C13—C14—S1—C8	179.7 (2)
C14—C9—C10—C11	0.1 (3)	C9—C14—S1—C8	0.24 (14)
C9—C10—C11—C12	−0.1 (3)	N1—C8—S1—C14	0.43 (15)
C10—C11—C12—C13	0.0 (4)	N2—C8—S1—C14	179.80 (15)
C11—C12—C13—C14	0.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.82	1.88	2.6034 (19)	147
C7—H7···O1ⁱ	0.93	2.43	3.309 (2)	158
C2—H2···N1ⁱⁱ	0.93	2.68	3.593 (2)	167

Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀N₂OS
M_r	254.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	12.150 (2), 8.9578 (15), 22.026 (4)
V (Å³)	2397.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.51 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12166, 2353, 1939
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.113, 1.06
No. of reflections	2353
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.24

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.82	1.88	2.6034 (19)	147
C7—H7···O1ⁱ	0.93	2.43	3.309 (2)	158
C2—H2···N1ⁱⁱ	0.93	2.68	3.593 (2)	167

Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) −x+2, y+1/2, −z+1/2.

Acknowledgements

The authors thank Dr Guangyou Zhang for help with the purification of the title compound.

References

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