2-Bromo-4-chloro-6-[(E)-o-tolyl­imino­meth­yl]phenol

Guo, J.-B.

doi:10.1107/S1600536810037931

organic compounds

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Volume 66| Part 10| October 2010| Page o2689

doi:10.1107/S1600536810037931

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2-Bromo-4-chloro-6-[(E)-o-tolyliminomethyl]phenol

Jin-Bao Guo ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji, Shaanxi 721007, People's Republic of China
^*Correspondence e-mail: guojinbao2010@126.com

(Received 20 September 2010; accepted 22 September 2010; online 30 September 2010)

The title compound, C₁₄H₁₁BrClNO, is a Schiff base compound derived from the condensation of 3-bromo-5-chlorosalicylaldehyde and o-toluidine in methanol. The aromatic rings make a dihedral angle of 38.3 (1)°. The molecular conformation is stabilized by an intramolecular O—H⋯N hydrogen bond, generating an S(6) ring.

Related literature

For Schiff bases, see: Ali et al. (2002 ). For related structures, see: Li & Zhang (2005 , 2006 ); Li et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₁BrClNO
M_r = 324.60
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.5388 (9) Å
b = 12.2452 (11) Å
c = 14.2440 (16) Å
V = 1314.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.32 mm⁻¹
T = 298 K
0.40 × 0.38 × 0.33 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.351, T_max = 0.408
5422 measured reflections
2284 independent reflections
1815 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.057
S = 1.09
2284 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 938 Friedel pairs
Flack parameter: 0.006 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.86	2.588 (3)	147

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); 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/S1600536810037931/bt5360sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037931/bt5360Isup2.hkl

checkCIF report

Comment top

The roles of Schiff base compounds in biological processes have become a topic of study in recent years. Schiff base compounds have demonstrated significant biological activity and new examples are being tested for their antitumor, antimicrobial, and antiviral activity (Ali et al., 2002). In the past years, we have prepared a series of Schiff base cmpounds, and investigated their structure and properties (Li et al., 2006; Li & Zhang, 2006; Li & Zhang, 2005).

In the title compound (Fig. 1), all the bond lengths and angles are within normal value and are comparable to those observed in a similar Schiff base compound (Li & Zhang, 2005). The two aromatic rings are linked by a C ═N bond and enclose a dihedral angle of 38.3 (1) °. As expected, the molecule adopts a trans configuration about the C1 ═N1 bond. The molecular conformation is stabilized by an intramolecular O—H–N hydrogen bond (Table 1).

Related literature top

For Schiff bases, see: Ali et al. (2002). For related structures, see: Li & Zhang (2005, 2006); Li et al. (2006).

Experimental top

3-bromo-5-Chlorosalicylaldehyde (0.1 mmol, 23.5 mg) and o-toluidine (0.1 mmol, 10.7 mg) dissolved in MeOH (10 ml). The solution was stirred for half an hour and then filtered. Crystals of the title compound suitable for single-crystal X-ray analysis were recrystallized from methanol after one weeks at room temperature. The yellow block precipitate was filtered, washed with cold MeOH, and dried in vacuo for 48 h (yield 70%).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. The dashed line indicates a hydrogen bond.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis.

2-Bromo-4-chloro-6-[(E)-o-tolyliminomethyl]phenol top

Crystal data top

C₁₄H₁₁BrClNO	D_x = 1.640 Mg m⁻³
M_r = 324.60	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 2013 reflections
a = 7.5388 (9) Å	θ = 2.2–23.7°
b = 12.2452 (11) Å	µ = 3.32 mm⁻¹
c = 14.2440 (16) Å	T = 298 K
V = 1314.9 (2) Å³	Block, yellow
Z = 4	0.40 × 0.38 × 0.33 mm
F(000) = 648

Data collection top

Bruker SMART CCD area-detector diffractometer	2284 independent reflections
Radiation source: fine-focus sealed tube	1815 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→8
T_min = 0.351, T_max = 0.408	k = −14→14
5422 measured reflections	l = −16→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0039P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2284 reflections	Δρ_max = 0.25 e Å⁻³
164 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 938 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (10)

Crystal data top

C₁₄H₁₁BrClNO	V = 1314.9 (2) Å³
M_r = 324.60	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.5388 (9) Å	µ = 3.32 mm⁻¹
b = 12.2452 (11) Å	T = 298 K
c = 14.2440 (16) Å	0.40 × 0.38 × 0.33 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2284 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1815 reflections with I > 2σ(I)
T_min = 0.351, T_max = 0.408	R_int = 0.031
5422 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.057	Δρ_max = 0.25 e Å⁻³
S = 1.09	Δρ_min = −0.33 e Å⁻³
2284 reflections	Absolute structure: Flack (1983), 938 Friedel pairs
164 parameters	Absolute structure parameter: 0.006 (10)
0 restraints

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
Br1	0.04915 (6)	0.84654 (3)	−0.29615 (2)	0.06176 (15)
Cl1	0.26999 (17)	1.17472 (7)	−0.05785 (7)	0.0692 (3)
N1	0.1302 (3)	0.6835 (2)	0.05868 (17)	0.0362 (7)
O1	0.0835 (3)	0.71558 (18)	−0.11917 (15)	0.0500 (7)
H1	0.0929	0.6804	−0.0704	0.075*
C1	0.1777 (5)	0.7832 (3)	0.0667 (2)	0.0388 (9)
H1A	0.2136	0.8093	0.1250	0.047*
C2	0.1770 (4)	0.8568 (3)	−0.0137 (2)	0.0339 (8)
C3	0.1263 (4)	0.8203 (3)	−0.1027 (2)	0.0376 (9)
C4	0.1196 (5)	0.8952 (3)	−0.1764 (2)	0.0400 (9)
C5	0.1624 (5)	1.0029 (3)	−0.1627 (2)	0.0450 (10)
H5	0.1554	1.0522	−0.2122	0.054*
C6	0.2160 (5)	1.0382 (3)	−0.0746 (2)	0.0447 (10)
C7	0.2229 (5)	0.9665 (3)	−0.0010 (2)	0.0408 (9)
H7	0.2583	0.9909	0.0579	0.049*
C8	0.1220 (5)	0.6153 (3)	0.1403 (2)	0.0364 (9)
C9	0.1705 (5)	0.5059 (3)	0.1305 (2)	0.0360 (9)
C10	0.1639 (5)	0.4404 (3)	0.2096 (3)	0.0477 (9)
H10	0.1993	0.3678	0.2053	0.057*
C11	0.1059 (5)	0.4805 (3)	0.2947 (3)	0.0516 (11)
H11	0.1014	0.4348	0.3467	0.062*
C12	0.0553 (5)	0.5866 (3)	0.3027 (2)	0.0478 (9)
H12	0.0163	0.6133	0.3602	0.057*
C13	0.0618 (5)	0.6549 (3)	0.22552 (19)	0.0415 (8)
H13	0.0259	0.7273	0.2309	0.050*
C14	0.2313 (6)	0.4607 (3)	0.0376 (2)	0.0600 (12)
H14A	0.2589	0.3845	0.0445	0.090*
H14B	0.3352	0.4993	0.0171	0.090*
H14C	0.1387	0.4692	−0.0081	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0701 (3)	0.0765 (3)	0.03869 (18)	0.0032 (3)	−0.0065 (2)	0.0004 (2)
Cl1	0.1052 (9)	0.0331 (5)	0.0692 (6)	−0.0064 (6)	−0.0041 (6)	0.0075 (5)
N1	0.0390 (18)	0.0323 (16)	0.0372 (15)	−0.0012 (14)	0.0006 (13)	0.0021 (14)
O1	0.064 (2)	0.0434 (14)	0.0423 (13)	−0.0024 (13)	−0.0035 (13)	−0.0011 (11)
C1	0.034 (2)	0.045 (2)	0.038 (2)	0.0001 (18)	0.0003 (18)	0.0037 (18)
C2	0.035 (2)	0.033 (2)	0.0335 (17)	0.0014 (19)	0.0021 (15)	0.0014 (18)
C3	0.033 (2)	0.034 (2)	0.046 (2)	0.0048 (17)	0.0093 (16)	−0.0010 (18)
C4	0.036 (2)	0.050 (2)	0.034 (2)	0.0074 (18)	0.0019 (16)	0.0027 (17)
C5	0.045 (3)	0.050 (2)	0.040 (2)	0.009 (2)	0.0088 (19)	0.0144 (19)
C6	0.045 (3)	0.038 (2)	0.050 (2)	0.001 (2)	0.0066 (19)	0.006 (2)
C7	0.045 (3)	0.041 (2)	0.0354 (19)	−0.002 (2)	0.0011 (17)	0.0011 (18)
C8	0.038 (2)	0.036 (2)	0.0354 (19)	−0.0042 (16)	−0.0018 (16)	0.0049 (16)
C9	0.039 (2)	0.030 (2)	0.0396 (19)	−0.0054 (18)	−0.0004 (18)	0.0001 (17)
C10	0.052 (3)	0.033 (2)	0.058 (2)	−0.0044 (18)	−0.001 (2)	0.004 (2)
C11	0.063 (3)	0.051 (3)	0.041 (2)	−0.010 (2)	−0.006 (2)	0.017 (2)
C12	0.054 (3)	0.053 (2)	0.0363 (19)	−0.012 (2)	0.005 (2)	0.0002 (19)
C13	0.049 (2)	0.0355 (19)	0.0402 (18)	0.002 (2)	0.0055 (17)	−0.0007 (17)
C14	0.075 (3)	0.050 (2)	0.055 (2)	0.000 (3)	0.015 (2)	0.000 (2)

Geometric parameters (Å, º) top

Br1—C4	1.883 (3)	C7—H7	0.9300
Cl1—C6	1.737 (4)	C8—C13	1.383 (4)
N1—C1	1.277 (4)	C8—C9	1.395 (4)
N1—C8	1.433 (4)	C9—C10	1.385 (4)
O1—C3	1.343 (4)	C9—C14	1.506 (5)
O1—H1	0.8200	C10—C11	1.378 (5)
C1—C2	1.458 (4)	C10—H10	0.9300
C1—H1A	0.9300	C11—C12	1.359 (5)
C2—C7	1.398 (5)	C11—H11	0.9300
C2—C3	1.398 (4)	C12—C13	1.382 (4)
C3—C4	1.394 (4)	C12—H12	0.9300
C4—C5	1.373 (5)	C13—H13	0.9300
C5—C6	1.386 (4)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.368 (4)	C14—H14C	0.9600

C1—N1—C8	119.8 (3)	C13—C8—N1	121.5 (3)
C3—O1—H1	109.5	C9—C8—N1	117.8 (3)
N1—C1—C2	121.3 (3)	C10—C9—C8	117.7 (3)
N1—C1—H1A	119.3	C10—C9—C14	120.8 (3)
C2—C1—H1A	119.3	C8—C9—C14	121.4 (3)
C7—C2—C3	119.4 (3)	C11—C10—C9	121.3 (3)
C7—C2—C1	119.5 (3)	C11—C10—H10	119.3
C3—C2—C1	121.1 (3)	C9—C10—H10	119.3
O1—C3—C4	119.2 (3)	C12—C11—C10	120.2 (3)
O1—C3—C2	121.9 (3)	C12—C11—H11	119.9
C4—C3—C2	118.9 (3)	C10—C11—H11	119.9
C5—C4—C3	121.0 (3)	C11—C12—C13	120.1 (3)
C5—C4—Br1	120.0 (3)	C11—C12—H12	119.9
C3—C4—Br1	119.0 (3)	C13—C12—H12	119.9
C4—C5—C6	119.8 (3)	C12—C13—C8	119.8 (3)
C4—C5—H5	120.1	C12—C13—H13	120.1
C6—C5—H5	120.1	C8—C13—H13	120.1
C7—C6—C5	120.3 (3)	C9—C14—H14A	109.5
C7—C6—Cl1	120.2 (3)	C9—C14—H14B	109.5
C5—C6—Cl1	119.5 (3)	H14A—C14—H14B	109.5
C6—C7—C2	120.5 (3)	C9—C14—H14C	109.5
C6—C7—H7	119.7	H14A—C14—H14C	109.5
C2—C7—H7	119.7	H14B—C14—H14C	109.5
C13—C8—C9	120.7 (3)

C8—N1—C1—C2	−176.1 (3)	Cl1—C6—C7—C2	179.0 (3)
N1—C1—C2—C7	177.3 (3)	C3—C2—C7—C6	0.9 (5)
N1—C1—C2—C3	−0.9 (5)	C1—C2—C7—C6	−177.3 (3)
C7—C2—C3—O1	179.0 (3)	C1—N1—C8—C13	38.4 (5)
C1—C2—C3—O1	−2.8 (5)	C1—N1—C8—C9	−144.0 (3)
C7—C2—C3—C4	−1.3 (5)	C13—C8—C9—C10	−2.8 (5)
C1—C2—C3—C4	176.9 (3)	N1—C8—C9—C10	179.5 (3)
O1—C3—C4—C5	−180.0 (3)	C13—C8—C9—C14	178.3 (3)
C2—C3—C4—C5	0.3 (5)	N1—C8—C9—C14	0.6 (5)
O1—C3—C4—Br1	0.4 (4)	C8—C9—C10—C11	2.1 (5)
C2—C3—C4—Br1	−179.4 (3)	C14—C9—C10—C11	−179.0 (3)
C3—C4—C5—C6	1.1 (5)	C9—C10—C11—C12	−0.7 (6)
Br1—C4—C5—C6	−179.3 (3)	C10—C11—C12—C13	0.0 (6)
C4—C5—C6—C7	−1.4 (6)	C11—C12—C13—C8	−0.8 (6)
C4—C5—C6—Cl1	180.0 (3)	C9—C8—C13—C12	2.2 (6)
C5—C6—C7—C2	0.4 (5)	N1—C8—C13—C12	179.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.86	2.588 (3)	147

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁BrClNO
M_r	324.60
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.5388 (9), 12.2452 (11), 14.2440 (16)
V (Å³)	1314.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.32
Crystal size (mm)	0.40 × 0.38 × 0.33

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.351, 0.408
No. of measured, independent and observed [I > 2σ(I)] reflections	5422, 2284, 1815
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.057, 1.09
No. of reflections	2284
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.33
Absolute structure	Flack (1983), 938 Friedel pairs
Absolute structure parameter	0.006 (10)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), 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···N1	0.82	1.86	2.588 (3)	147

Acknowledgements

This research was supported by a research grant (No. 09JS068) from the Phytochemistry Key Laboratory of Shaanxi Province.

References

Ali, M. A., Mirza, A. H., Butcher, R. J., Tarafder, M. T. H. & Keat, T. B. (2002). J. Inorg. Biochem. 92, 141–148. CSD CrossRef PubMed Google Scholar
Bruker (2003). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, Z. X. & Zhang, X. L. (2005). Chin. J. Struct. Chem. 11, 1310–1313. Google Scholar
Li, Z.-X. & Zhang, X.-L. (2006). Acta Cryst. E62, o1738–o1739. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Z.-X., Zhang, X.-L. & Wang, X.-L. (2006). Acta Cryst. E62, o4513–o4514. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar