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

Zhang, X.

doi:10.1107/S1600536809003912

organic compounds

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Volume 65| Part 3| March 2009| Page o513

doi:10.1107/S1600536809003912

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

Xinli Zhang ^a ^*

^aDepartment of Chemistry, Baoji University of Arts and Science, Baoji, Shaanxi 721007, People's Republic of China
^*Correspondence e-mail: zhangxinli6008@163.com

(Received 1 January 2009; accepted 2 February 2009; online 11 February 2009)

The molecule of the title compound, C₁₄H₁₁BrClNO, displays an E configuration with respect to the imine C=N double bond. The two aromatic rings are essentially coplanar, forming a dihedral angle of 7.9 (2)°. An intramolecular O—H⋯N hydrogen bond stabilizes the crystal structure.

Related literature

For the role of Schiff base ligands in catalysis and electron transfer in living organisms, see: Ueno et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₁BrClNO
M_r = 324.60
Triclinic, $[P \overline 1]$
a = 8.1354 (14) Å
b = 8.6844 (17) Å
c = 11.3740 (18) Å
α = 76.040 (2)°
β = 73.652 (12)°
γ = 62.458 (12)°
V = 677.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.22 mm⁻¹
T = 298 (2) K
0.43 × 0.18 × 0.09 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.332, T_max = 0.745
3500 measured reflections
2351 independent reflections
1412 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.129
S = 1.00
2351 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.43 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	1.84	2.574 (4)	148

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); 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/S1600536809003912/rz2287sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003912/rz2287Isup2.hkl

checkCIF report

Comment top

Recently, there has been a growing interest in Schiff base ligands because of their applications, such as catalysts and non-linear optical materials. In recent years, they were found to play an important role in the catalysis and electron transfer of the living organisms (Ueno et al., 2006). This stimulated our interest in this field. As an extension of the work on the structural characterization of Schiff base compounds, the crystal structure of the title compound is reported here.

The molecular structure and crystal packing of the title compound are illustrated in Figure 1 and 2, respectively. Bond lengths and angles are not unusual, with the C1═N1 bond distance (1.263 (5) Å) slightly shorter than a normal C═N. The molecule is essentially planar, the maximum deviation from the planarity being 0.167 (6) Å for atom C10. The dihedral angle between the two aromatic rings is 7.9 (2) °. An intramolecular O—H···N hydrogen bond (Table 1) stabilizes the crystal structure.

Related literature top

For the role of Schiff base ligands in the catalysis and electron transfer of living organisms, see: Ueno et al. (2006).

Experimental top

3-Bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.6 mg) and p-toluidine (0.1 mmol, 10.7 mg) were dissolved in methanol (10 ml). The mixture was stirred at room temperature for 10 min and then filtered. After allowing the filtrate to stand in air for 3 d, yellow block-shaped crystals of the title compound suitable for X-ray analysis were formed by slow evaporation of the solvent. The crystals were collected, washed with methanol and dried in a vacuum desiccator using anhydrous CaCl₂ (yield 54%).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 with 30% probability ellipsoids. H atoms are shown as spheres of arbitrary radii. The dashed line represents a hydrogen bond.
	Fig. 2. The crystal packing of the title compound viewed along the b axis.

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

Crystal data top

C₁₄H₁₁BrClNO	Z = 2
M_r = 324.60	F(000) = 324
Triclinic, P1	D_x = 1.590 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1354 (14) Å	Cell parameters from 1148 reflections
b = 8.6844 (17) Å	θ = 2.7–24.9°
c = 11.3740 (18) Å	µ = 3.22 mm⁻¹
α = 76.040 (2)°	T = 298 K
β = 73.652 (12)°	Block-shaped, yellow
γ = 62.458 (12)°	0.43 × 0.18 × 0.09 mm
V = 677.9 (2) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	2351 independent reflections
Radiation source: fine-focus sealed tube	1412 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −9→9
T_min = 0.332, T_max = 0.745	k = −6→10
3500 measured reflections	l = −13→13

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) = 0.129	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.065P)²] where P = (F_o² + 2F_c²)/3
2351 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₄H₁₁BrClNO	γ = 62.458 (12)°
M_r = 324.60	V = 677.9 (2) Å³
Triclinic, P1	Z = 2
a = 8.1354 (14) Å	Mo Kα radiation
b = 8.6844 (17) Å	µ = 3.22 mm⁻¹
c = 11.3740 (18) Å	T = 298 K
α = 76.040 (2)°	0.43 × 0.18 × 0.09 mm
β = 73.652 (12)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2351 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	1412 reflections with I > 2σ(I)
T_min = 0.332, T_max = 0.745	R_int = 0.028
3500 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.00	Δρ_max = 0.51 e Å⁻³
2351 reflections	Δρ_min = −0.43 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
Br1	0.62666 (9)	0.48664 (8)	0.11313 (5)	0.0881 (3)
Cl1	0.2620 (2)	1.09756 (16)	0.31821 (13)	0.0714 (4)
O1	0.7924 (4)	0.3591 (4)	0.3427 (3)	0.0554 (9)
H1	0.8367	0.3272	0.4054	0.083*
N1	0.8449 (5)	0.3835 (5)	0.5491 (3)	0.0414 (9)
C1	0.7224 (6)	0.5406 (6)	0.5417 (4)	0.0434 (11)
H1A	0.6902	0.6050	0.6058	0.052*
C2	0.6298 (6)	0.6243 (6)	0.4356 (4)	0.0381 (10)
C3	0.6708 (6)	0.5270 (6)	0.3398 (4)	0.0387 (10)
C4	0.5770 (6)	0.6130 (6)	0.2422 (4)	0.0439 (11)
C5	0.4522 (6)	0.7843 (6)	0.2351 (4)	0.0457 (11)
H5	0.3916	0.8380	0.1683	0.055*
C6	0.4168 (6)	0.8776 (6)	0.3294 (4)	0.0467 (11)
C7	0.5034 (6)	0.7974 (6)	0.4289 (4)	0.0476 (11)
H7	0.4763	0.8608	0.4925	0.057*
C8	0.9370 (6)	0.3016 (6)	0.6518 (4)	0.0416 (11)
C9	0.9271 (7)	0.3898 (7)	0.7423 (4)	0.0553 (13)
H9	0.8552	0.5102	0.7394	0.066*
C10	1.0267 (7)	0.2956 (8)	0.8377 (4)	0.0619 (14)
H10	1.0201	0.3549	0.8981	0.074*
C11	1.1339 (7)	0.1177 (7)	0.8446 (4)	0.0541 (13)
C12	1.1407 (7)	0.0343 (7)	0.7539 (4)	0.0604 (14)
H12	1.2122	−0.0862	0.7571	0.072*
C13	1.0454 (6)	0.1229 (6)	0.6584 (4)	0.0522 (12)
H13	1.0540	0.0623	0.5981	0.063*
C14	1.2405 (8)	0.0205 (8)	0.9481 (4)	0.0813 (18)
H14A	1.2169	0.1011	1.0021	0.122*
H14B	1.3735	−0.0336	0.9144	0.122*
H14C	1.1990	−0.0679	0.9938	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1111 (6)	0.0784 (5)	0.0686 (4)	−0.0123 (4)	−0.0436 (4)	−0.0269 (3)
Cl1	0.0773 (9)	0.0392 (7)	0.0848 (9)	−0.0057 (7)	−0.0321 (8)	−0.0064 (6)
O1	0.058 (2)	0.0406 (19)	0.0586 (19)	−0.0026 (17)	−0.0275 (16)	−0.0109 (15)
N1	0.037 (2)	0.042 (2)	0.046 (2)	−0.0165 (19)	−0.0143 (17)	0.0014 (17)
C1	0.047 (3)	0.046 (3)	0.042 (2)	−0.023 (3)	−0.010 (2)	−0.005 (2)
C2	0.036 (2)	0.041 (3)	0.043 (2)	−0.021 (2)	−0.010 (2)	−0.002 (2)
C3	0.033 (2)	0.039 (3)	0.046 (2)	−0.015 (2)	−0.011 (2)	−0.004 (2)
C4	0.043 (3)	0.047 (3)	0.042 (2)	−0.015 (2)	−0.011 (2)	−0.011 (2)
C5	0.042 (3)	0.048 (3)	0.048 (3)	−0.020 (2)	−0.017 (2)	0.004 (2)
C6	0.045 (3)	0.042 (3)	0.053 (3)	−0.020 (2)	−0.015 (2)	0.002 (2)
C7	0.051 (3)	0.040 (3)	0.055 (3)	−0.018 (2)	−0.015 (2)	−0.009 (2)
C8	0.034 (2)	0.052 (3)	0.041 (2)	−0.023 (2)	−0.012 (2)	0.004 (2)
C9	0.056 (3)	0.053 (3)	0.055 (3)	−0.019 (3)	−0.024 (2)	0.002 (2)
C10	0.062 (3)	0.087 (4)	0.052 (3)	−0.040 (3)	−0.019 (3)	−0.008 (3)
C11	0.049 (3)	0.068 (4)	0.047 (3)	−0.031 (3)	−0.020 (2)	0.016 (3)
C12	0.061 (3)	0.047 (3)	0.069 (3)	−0.021 (3)	−0.029 (3)	0.016 (3)
C13	0.053 (3)	0.048 (3)	0.055 (3)	−0.018 (3)	−0.019 (2)	−0.003 (2)
C14	0.080 (4)	0.110 (5)	0.061 (3)	−0.052 (4)	−0.037 (3)	0.028 (3)

Geometric parameters (Å, º) top

Br1—C4	1.885 (4)	C7—H7	0.9300
Cl1—C6	1.732 (5)	C8—C13	1.381 (6)
O1—C3	1.329 (5)	C8—C9	1.389 (6)
O1—H1	0.8200	C9—C10	1.399 (6)
N1—C1	1.263 (5)	C9—H9	0.9300
N1—C8	1.425 (5)	C10—C11	1.374 (7)
C1—C2	1.462 (5)	C10—H10	0.9300
C1—H1A	0.9300	C11—C12	1.372 (7)
C2—C7	1.372 (6)	C11—C14	1.506 (6)
C2—C3	1.411 (5)	C12—C13	1.376 (6)
C3—C4	1.387 (5)	C12—H12	0.9300
C4—C5	1.357 (6)	C13—H13	0.9300
C5—C6	1.386 (6)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.370 (6)	C14—H14C	0.9600

C3—O1—H1	109.5	C13—C8—N1	116.6 (4)
C1—N1—C8	122.3 (4)	C9—C8—N1	124.4 (4)
N1—C1—C2	121.9 (4)	C8—C9—C10	119.3 (5)
N1—C1—H1A	119.0	C8—C9—H9	120.4
C2—C1—H1A	119.0	C10—C9—H9	120.4
C7—C2—C3	120.0 (4)	C11—C10—C9	121.8 (5)
C7—C2—C1	120.0 (4)	C11—C10—H10	119.1
C3—C2—C1	119.9 (4)	C9—C10—H10	119.1
O1—C3—C4	120.8 (4)	C12—C11—C10	117.6 (4)
O1—C3—C2	121.9 (4)	C12—C11—C14	122.0 (5)
C4—C3—C2	117.3 (4)	C10—C11—C14	120.4 (5)
C5—C4—C3	122.8 (4)	C11—C12—C13	122.2 (5)
C5—C4—Br1	118.7 (3)	C11—C12—H12	118.9
C3—C4—Br1	118.5 (3)	C13—C12—H12	118.9
C4—C5—C6	118.7 (4)	C12—C13—C8	120.2 (5)
C4—C5—H5	120.7	C12—C13—H13	119.9
C6—C5—H5	120.7	C8—C13—H13	119.9
C7—C6—C5	120.5 (4)	C11—C14—H14A	109.5
C7—C6—Cl1	120.9 (4)	C11—C14—H14B	109.5
C5—C6—Cl1	118.5 (3)	H14A—C14—H14B	109.5
C6—C7—C2	120.6 (4)	C11—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	119.0 (4)

C8—N1—C1—C2	179.4 (4)	Cl1—C6—C7—C2	−178.2 (3)
N1—C1—C2—C7	−177.3 (4)	C3—C2—C7—C6	−0.4 (6)
N1—C1—C2—C3	2.6 (6)	C1—C2—C7—C6	179.5 (4)
C7—C2—C3—O1	179.9 (4)	C1—N1—C8—C13	170.2 (4)
C1—C2—C3—O1	0.1 (6)	C1—N1—C8—C9	−11.1 (6)
C7—C2—C3—C4	−0.8 (6)	C13—C8—C9—C10	−0.2 (7)
C1—C2—C3—C4	179.3 (4)	N1—C8—C9—C10	−178.8 (4)
O1—C3—C4—C5	−179.8 (4)	C8—C9—C10—C11	−0.1 (7)
C2—C3—C4—C5	1.0 (6)	C9—C10—C11—C12	0.1 (7)
O1—C3—C4—Br1	−0.2 (6)	C9—C10—C11—C14	179.5 (4)
C2—C3—C4—Br1	−179.5 (3)	C10—C11—C12—C13	0.2 (7)
C3—C4—C5—C6	0.1 (7)	C14—C11—C12—C13	−179.2 (4)
Br1—C4—C5—C6	−179.5 (3)	C11—C12—C13—C8	−0.5 (7)
C4—C5—C6—C7	−1.3 (6)	C9—C8—C13—C12	0.5 (7)
C4—C5—C6—Cl1	178.4 (3)	N1—C8—C13—C12	179.2 (4)
C5—C6—C7—C2	1.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.84	2.574 (4)	148

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁BrClNO
M_r	324.60
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.1354 (14), 8.6844 (17), 11.3740 (18)
α, β, γ (°)	76.040 (2), 73.652 (12), 62.458 (12)
V (Å³)	677.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.22
Crystal size (mm)	0.43 × 0.18 × 0.09

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.332, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	3500, 2351, 1412
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.129, 1.00
No. of reflections	2351
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.43

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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	1.84	2.574 (4)	148.0

Acknowledgements

The author gratefully acknowledges support from a research project (No. 08JZ09) of the Phytochemistry Key Laboratory of Shaanxi Province.

References

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Ueno, T., Yokoi, N., Unno, M., Matsui, T., Tokita, Y., Yamada, M., Ikeda-Saito, M., Nakajima, H. & Watanabe, Y. (2006). PNAS, 103, 9416–9421. Web of Science CrossRef PubMed CAS Google Scholar