2-Bromo-4-chloro-6-[(1-phenyl­ethyl)­imino­meth­yl]phenol

Zhang, X.

doi:10.1107/S1600536808031383

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2084

doi:10.1107/S1600536808031383

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2-Bromo-4-chloro-6-[(1-phenylethyl)iminomethyl]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 30 July 2008; accepted 28 September 2008; online 9 October 2008)

The title compound, C₁₅H₁₃BrClNO, is a Schiff base derived from the condensation of equimolar quantities of 3-bromo-5-chlorosalicylaldehyde and 1-phenylethanamine. The structure displays a trans configuration with respect to the imine C=N double bond. The N atom is also involved in an intramolecular O—H—N hydrogen bond, which stabilizes the configuration of the compound.

Related literature

Schiff base ligands have demonstrated significant biological activities and new examples are being tested for their antimicrobial activity (Ali et al., 2002 ; Cukurovali et al., 2002 ) and antiviral activity (Tarafder et al., 2002 ).

Experimental

Crystal data

C₁₅H₁₃BrClNO
M_r = 338.62
Monoclinic, C 2/c
a = 21.764 (2) Å
b = 9.5088 (13) Å
c = 15.3591 (16) Å
β = 113.426 (2)°
V = 2916.6 (6) Å³
Z = 8
Mo Kα radiation
μ = 2.99 mm⁻¹
T = 298 (2) K
0.36 × 0.22 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.412, T_max = 0.600 (expected range = 0.389–0.566)
7192 measured reflections
2574 independent reflections
1377 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.108
S = 1.00
2574 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.37 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	2.591 (4)	147

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/S1600536808031383/gw2049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031383/gw2049Isup2.hkl

checkCIF report

Comment top

In recent years, the role of Schiff base and its derivatives in biological processes have become a topic of study. Schiff base ligands have demonstrated significant biological activities and new examples are being tested for their antitumor, antimicrobial and antiviral activities (Tarafder et al., 2002; Cukurovali et al., 2002; Ali et al., 2002). These properties stimulated our interest in this field. Crystals of the title compound, (I), were obtained as a new Schiff base compound. The title compound (I) is an 3-bromine-5-chloro-salicylaldehyde derivative. All bond lengths and bond angles are in the normal ranges and comparable to those observed in a similar salicylaldehyde Schiff base. its molecular Structure and a Crystal packing are illusrated in Figs. 1 and 2, respectively. The C1═N1 bond length of 1.257 (5) Å conforms to the value for a double bond. The torsional angles of C8—N1–2 and N1—C1—C2—C7 are 176.5 (4)° and -175.6 (4)°, respectively. Atom O1 deviates from the benzene mean plane by 0.026 (3)°, whereas atoms Br and Cl by 0.072 (4)° and 0.047 (4)°, respectively. The molecular structure adopts a trans configuration about the C1═N1 bond. In the molecule, there exists a intramolecular O—H—N hydrogen bond involving hydroxy atom O1 and imine atom N1 (Table 1). Furthermore, a more interesting phenomenon observed is shown in Fig. 2. Pairs of phen ligands from neighbouring complexes are interleaved to form a pi–pi stacking along the c axis. The distance between two phen ring Centroids are 3.744 (3) Å indicating significant pi–pi stacking packing interactions. The structure of (I) is thus stabilized by the hydrogen-bond system and aromatic-ring stacking interactions.

Related literature top

For related literature, see: Ali et al. (2002); Cukurovali et al. (2002); Tarafder et al. (2002). From the Section Editors: It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···." etc. Please revise this section as indicated.

Experimental top

3-bromine-5-Chlorosalicylaldehyde (0.1 mmol, 23.55 mg) and 1-phenylethanamine (0.1 mmol, 12.1 mg) were dissolved in methanol (10 ml). The mixture was stirred for 30 min at room temperature to give a clear brown solution. After allowing the resulting solution to stand in air for 7 d, yellow block-shaped crystals of (I) were formed on slow evaporation of the solvent. The crystals were collected, washed with methanol and dried in a vacuum desiccator using anhydrous CaCl₂ (yield 54%). Analysis found: C 46.32%, H 3.35%, calculated for C₁₅H₁₃Br_ClN_O: C 46.33%, H 3.35%.

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. The structure of the title compound in 30% probability ellipsoids. H atoms are shown as spheres of arbitrary radii. The dotted line represent a hydrogen bond.
	Fig. 2. The molecular packing of (I) viewed along the b axis.

2-Bromo-4-chloro-6-[(1-phenylethyl)iminomethyl]phenol top

Crystal data top

C₁₅H₁₃BrClNO	F(000) = 1360
M_r = 338.62	D_x = 1.542 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.764 (2) Å	Cell parameters from 1447 reflections
b = 9.5088 (13) Å	θ = 2.4–21.8°
c = 15.3591 (16) Å	µ = 2.99 mm⁻¹
β = 113.426 (2)°	T = 298 K
V = 2916.6 (6) Å³	Block, yellow
Z = 8	0.36 × 0.22 × 0.19 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2574 independent reflections
Radiation source: fine-focus sealed tube	1377 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
T_min = 0.412, T_max = 0.600	k = −9→11
7192 measured reflections	l = −17→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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0381P)² + 4.3819P] where P = (F_o² + 2F_c²)/3
2574 reflections	(Δ/σ)_max = 0.002
172 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₅H₁₃BrClNO	V = 2916.6 (6) Å³
M_r = 338.62	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.764 (2) Å	µ = 2.99 mm⁻¹
b = 9.5088 (13) Å	T = 298 K
c = 15.3591 (16) Å	0.36 × 0.22 × 0.19 mm
β = 113.426 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2574 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1377 reflections with I > 2σ(I)
T_min = 0.412, T_max = 0.600	R_int = 0.038
7192 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.00	Δρ_max = 0.41 e Å⁻³
2574 reflections	Δρ_min = −0.37 e Å⁻³
172 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	1.16005 (2)	0.40337 (6)	0.56363 (4)	0.0873 (3)
Cl1	1.03028 (8)	0.89286 (15)	0.39942 (12)	0.1095 (6)
N1	0.91088 (17)	0.2822 (5)	0.2946 (2)	0.0644 (11)
O1	1.03226 (14)	0.2790 (3)	0.4226 (2)	0.0702 (9)
H1	0.9971	0.2461	0.3842	0.105*
C1	0.9157 (2)	0.4134 (6)	0.2895 (3)	0.0638 (13)
H1A	0.8799	0.4629	0.2457	0.077*
C2	0.9755 (2)	0.4910 (5)	0.3496 (3)	0.0554 (12)
C3	1.0310 (2)	0.4192 (5)	0.4141 (3)	0.0526 (11)
C4	1.08586 (19)	0.4972 (5)	0.4726 (3)	0.0545 (11)
C5	1.0864 (2)	0.6413 (5)	0.4677 (3)	0.0583 (12)
H5	1.1236	0.6919	0.5071	0.070*
C6	1.0313 (2)	0.7100 (5)	0.4038 (3)	0.0646 (13)
C7	0.9767 (2)	0.6361 (5)	0.3458 (3)	0.0662 (13)
H7	0.9397	0.6840	0.3031	0.079*
C8	0.8465 (2)	0.2157 (5)	0.2340 (3)	0.0716 (15)
H8	0.8179	0.2867	0.1903	0.086*
C9	0.8613 (3)	0.1015 (6)	0.1769 (4)	0.101 (2)
H9A	0.8795	0.1429	0.1352	0.151*
H9B	0.8208	0.0522	0.1401	0.151*
H9C	0.8932	0.0369	0.2191	0.151*
C10	0.8132 (2)	0.1667 (5)	0.2970 (3)	0.0535 (12)
C11	0.7589 (3)	0.2392 (6)	0.2985 (3)	0.0720 (14)
H11	0.7422	0.3159	0.2585	0.086*
C12	0.7289 (3)	0.1996 (8)	0.3585 (5)	0.0954 (19)
H12	0.6926	0.2505	0.3592	0.114*
C13	0.7519 (4)	0.0872 (8)	0.4165 (4)	0.096 (2)
H13	0.7311	0.0603	0.4562	0.115*
C14	0.8051 (4)	0.0142 (6)	0.4165 (4)	0.0885 (18)
H14	0.8213	−0.0624	0.4569	0.106*
C15	0.8358 (3)	0.0533 (6)	0.3563 (4)	0.0729 (14)
H15	0.8721	0.0019	0.3562	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0491 (3)	0.0926 (4)	0.1028 (5)	0.0052 (3)	0.0120 (3)	0.0109 (3)
Cl1	0.0987 (11)	0.0682 (9)	0.1278 (14)	−0.0118 (8)	0.0094 (9)	0.0236 (9)
N1	0.060 (2)	0.077 (3)	0.054 (2)	−0.018 (2)	0.0212 (19)	−0.011 (2)
O1	0.0555 (19)	0.068 (2)	0.084 (2)	−0.0020 (16)	0.0243 (17)	−0.0038 (18)
C1	0.054 (3)	0.087 (4)	0.047 (3)	−0.008 (3)	0.016 (2)	0.003 (3)
C2	0.048 (3)	0.080 (4)	0.040 (3)	−0.007 (2)	0.020 (2)	0.000 (2)
C3	0.056 (3)	0.060 (3)	0.056 (3)	−0.005 (3)	0.037 (2)	−0.004 (2)
C4	0.042 (2)	0.070 (3)	0.055 (3)	−0.001 (2)	0.023 (2)	0.001 (2)
C5	0.052 (3)	0.073 (3)	0.052 (3)	−0.016 (2)	0.023 (2)	−0.003 (2)
C6	0.063 (3)	0.069 (3)	0.059 (3)	−0.014 (3)	0.020 (3)	0.006 (3)
C7	0.061 (3)	0.077 (4)	0.056 (3)	0.002 (3)	0.018 (2)	0.015 (3)
C8	0.062 (3)	0.092 (4)	0.052 (3)	−0.021 (3)	0.012 (3)	−0.005 (3)
C9	0.096 (4)	0.142 (5)	0.079 (4)	−0.043 (4)	0.050 (3)	−0.052 (4)
C10	0.051 (3)	0.064 (3)	0.038 (2)	−0.012 (2)	0.010 (2)	−0.006 (2)
C11	0.064 (3)	0.077 (4)	0.061 (3)	−0.006 (3)	0.010 (3)	−0.004 (3)
C12	0.067 (4)	0.120 (6)	0.100 (5)	−0.015 (4)	0.035 (4)	−0.037 (4)
C13	0.108 (5)	0.113 (6)	0.076 (4)	−0.046 (5)	0.047 (4)	−0.023 (4)
C14	0.126 (5)	0.066 (4)	0.060 (4)	−0.021 (4)	0.023 (4)	−0.003 (3)
C15	0.078 (3)	0.078 (4)	0.060 (3)	−0.002 (3)	0.024 (3)	−0.009 (3)

Geometric parameters (Å, º) top

Br1—C4	1.888 (4)	C8—C9	1.510 (7)
Cl1—C6	1.740 (5)	C8—H8	0.9800
N1—C1	1.257 (5)	C9—H9A	0.9600
N1—C8	1.481 (5)	C9—H9B	0.9600
O1—C3	1.339 (5)	C9—H9C	0.9600
O1—H1	0.8200	C10—C15	1.371 (6)
C1—C2	1.462 (6)	C10—C11	1.377 (6)
C1—H1A	0.9300	C11—C12	1.375 (7)
C2—C7	1.382 (6)	C11—H11	0.9300
C2—C3	1.398 (6)	C12—C13	1.354 (8)
C3—C4	1.389 (5)	C12—H12	0.9300
C4—C5	1.372 (6)	C13—C14	1.350 (8)
C5—C6	1.376 (6)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.390 (8)
C6—C7	1.363 (6)	C14—H14	0.9300
C7—H7	0.9300	C15—H15	0.9300
C8—C10	1.494 (6)

C1—N1—C8	117.8 (4)	C10—C8—H8	108.7
C3—O1—H1	109.5	C9—C8—H8	108.7
N1—C1—C2	122.5 (4)	C8—C9—H9A	109.5
N1—C1—H1A	118.7	C8—C9—H9B	109.5
C2—C1—H1A	118.7	H9A—C9—H9B	109.5
C7—C2—C3	119.5 (4)	C8—C9—H9C	109.5
C7—C2—C1	120.3 (4)	H9A—C9—H9C	109.5
C3—C2—C1	120.2 (4)	H9B—C9—H9C	109.5
O1—C3—C4	119.3 (4)	C15—C10—C11	117.8 (5)
O1—C3—C2	122.3 (4)	C15—C10—C8	122.5 (5)
C4—C3—C2	118.4 (4)	C11—C10—C8	119.7 (5)
C5—C4—C3	121.4 (4)	C12—C11—C10	120.9 (5)
C5—C4—Br1	119.3 (3)	C12—C11—H11	119.5
C3—C4—Br1	119.3 (4)	C10—C11—H11	119.5
C4—C5—C6	119.3 (4)	C13—C12—C11	120.4 (6)
C4—C5—H5	120.4	C13—C12—H12	119.8
C6—C5—H5	120.4	C11—C12—H12	119.8
C7—C6—C5	120.5 (4)	C14—C13—C12	119.9 (6)
C7—C6—Cl1	119.7 (4)	C14—C13—H13	120.0
C5—C6—Cl1	119.7 (4)	C12—C13—H13	120.0
C6—C7—C2	120.9 (4)	C13—C14—C15	120.1 (6)
C6—C7—H7	119.6	C13—C14—H14	120.0
C2—C7—H7	119.6	C15—C14—H14	120.0
N1—C8—C10	107.9 (3)	C10—C15—C14	120.8 (5)
N1—C8—C9	107.7 (4)	C10—C15—H15	119.6
C10—C8—C9	115.0 (4)	C14—C15—H15	119.6
N1—C8—H8	108.7

C8—N1—C1—C2	176.5 (4)	C3—C2—C7—C6	0.3 (7)
N1—C1—C2—C7	−175.6 (4)	C1—C2—C7—C6	177.8 (4)
N1—C1—C2—C3	1.9 (7)	C1—N1—C8—C10	−109.5 (5)
C7—C2—C3—O1	178.5 (4)	C1—N1—C8—C9	125.8 (5)
C1—C2—C3—O1	1.0 (6)	N1—C8—C10—C15	−72.1 (6)
C7—C2—C3—C4	0.0 (6)	C9—C8—C10—C15	48.1 (6)
C1—C2—C3—C4	−177.6 (4)	N1—C8—C10—C11	106.0 (5)
O1—C3—C4—C5	−178.8 (4)	C9—C8—C10—C11	−133.8 (5)
C2—C3—C4—C5	−0.3 (6)	C15—C10—C11—C12	0.7 (7)
O1—C3—C4—Br1	−1.0 (5)	C8—C10—C11—C12	−177.5 (4)
C2—C3—C4—Br1	177.6 (3)	C10—C11—C12—C13	−0.8 (8)
C3—C4—C5—C6	0.3 (7)	C11—C12—C13—C14	0.8 (8)
Br1—C4—C5—C6	−177.5 (3)	C12—C13—C14—C15	−0.8 (8)
C4—C5—C6—C7	−0.1 (7)	C11—C10—C15—C14	−0.7 (7)
C4—C5—C6—Cl1	178.0 (3)	C8—C10—C15—C14	177.5 (4)
C5—C6—C7—C2	−0.2 (7)	C13—C14—C15—C10	0.7 (8)
Cl1—C6—C7—C2	−178.3 (4)

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	2.591 (4)	147

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃BrClNO
M_r	338.62
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	21.764 (2), 9.5088 (13), 15.3591 (16)
β (°)	113.426 (2)
V (Å³)	2916.6 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.99
Crystal size (mm)	0.36 × 0.22 × 0.19

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.412, 0.600
No. of measured, independent and observed [I > 2σ(I)] reflections	7192, 2574, 1377
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.108, 1.00
No. of reflections	2574
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.37

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···N1	0.82	1.87	2.591 (4)	146.9

Acknowledgements

The author is grateful for a research grant (No. 08JZ09) supported by the Phytochemistry Key Laboratory of Shaanxi province.

References

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