2-Benzyl­imino­meth­yl-6-bromo-4-chloro­phenol

Pu, X.-H.

doi:10.1107/S1600536808024884

organic compounds

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Volume 64| Part 9| September 2008| Page o1734

doi:10.1107/S1600536808024884

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2-Benzyliminomethyl-6-bromo-4-chlorophenol

Xiao-Hua Pu ^a ^*

^aDepartment of Chemistry, Baoji University of Arts and Science, Baoji, Shaanxi 721007, People's Republic of China
^*Correspondence e-mail: pxh913@163.com

(Received 29 July 2008; accepted 2 August 2008; online 9 August 2008)

The title molecule, C₁₄H₁₁BrClNO, adopts a trans configuration with respect to the C=N double bond. The dihedral angle between the two aromatic rings is 70.4 (5)°. An intramolecular O—H⋯N hydrogen bond is observed between the hydroxyl and imine groups.

Related literature

For related literature, see: Ali et al. (2002 ); Cukurovali et al. (2002 ); Tarafder et al. (2002 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₁BrClNO
M_r = 324.60
Monoclinic, P 2₁ /c
a = 4.3334 (8) Å
b = 12.8976 (14) Å
c = 23.892 (2) Å
β = 92.992 (1)°
V = 1333.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.27 mm⁻¹
T = 298 (2) K
0.40 × 0.37 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.355, T_max = 0.676
6753 measured reflections
2325 independent reflections
1699 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.176
S = 1.06
2325 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 1.47 e Å⁻³
Δρ_min = −0.76 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	1.86	2.590 (7)	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/S1600536808024884/ci2649sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024884/ci2649Isup2.hkl

checkCIF report

Comment top

Schiff base compounds have been of great interest for many years. These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures. As an extension of the work on the structural characterization of Schiff base compounds, the crystal structure of the title compound is reported here.

Bond lengths in the title molecule (Fig. 1) have normal values (Allen et al.,1987). The C1═N1 bond length of 1.267 (9) Å conforms to the value for a double bond. The dihedral angle between the two aromatic rings is 70.4 (5)°. As expected, the molecule adopts a trans configuration about the C═N bond [C8—N1—C1—C2 = -178.6 (6)°]. An intramolecular O—H···N hydrogen bond is observed between hydroxyl and imine groups (Table 1).

Related literature top

For related literature, see: Ali et al. (2002); Cukurovali et al. (2002); Tarafder et al. (2002). For bond-length data, see: Allen et al. (1987).

Experimental top

3-Bromine-5-chlorosalicylaldehyde (0.1 mmol, 23.55 mg) and 1-benzylamine (0.1 mmol, 10.7 mg) were added to 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 the title compound 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 51.76, H 4.0%; calculated for C₁₄H₁₁Br_ClN_O: C 51.77, H 3.39%.

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 molecular structure of the title compound, showing 30% probability ellipsoids. The dashed line represents a hydrogen bond.
	Fig. 2. The crystal packing of the title compound, viewed down the b axis.

2-Benzyliminomethyl-6-bromo-4-chlorophenol top

Crystal data top

C₁₄H₁₁BrClNO	F(000) = 648
M_r = 324.60	D_x = 1.617 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2314 reflections
a = 4.3334 (8) Å	θ = 3.0–23.6°
b = 12.8976 (14) Å	µ = 3.27 mm⁻¹
c = 23.892 (2) Å	T = 298 K
β = 92.992 (1)°	Block, yellow
V = 1333.5 (3) Å³	0.40 × 0.37 × 0.13 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2325 independent reflections
Radiation source: fine-focus sealed tube	1699 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
T_min = 0.355, T_max = 0.676	k = −14→15
6753 measured reflections	l = −28→19

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0638P)² + 4.7838P] where P = (F_o² + 2F_c²)/3
2325 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 1.47 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₁₄H₁₁BrClNO	V = 1333.5 (3) Å³
M_r = 324.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.3334 (8) Å	µ = 3.27 mm⁻¹
b = 12.8976 (14) Å	T = 298 K
c = 23.892 (2) Å	0.40 × 0.37 × 0.13 mm
β = 92.992 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2325 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1699 reflections with I > 2σ(I)
T_min = 0.355, T_max = 0.676	R_int = 0.068
6753 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.06	Δρ_max = 1.47 e Å⁻³
2325 reflections	Δρ_min = −0.76 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
Br1	1.1330 (2)	0.05445 (6)	0.34840 (4)	0.0688 (3)
Cl1	1.1495 (6)	0.47661 (15)	0.37758 (10)	0.0761 (6)
N1	0.4056 (13)	0.2399 (4)	0.1816 (2)	0.0495 (14)
O1	0.7218 (12)	0.1150 (3)	0.2472 (2)	0.0588 (13)
H1	0.6061	0.1323	0.2205	0.088*
C1	0.4902 (15)	0.3140 (6)	0.2137 (3)	0.0465 (16)
H1A	0.4104	0.3798	0.2062	0.056*
C2	0.7087 (14)	0.3002 (5)	0.2620 (3)	0.0409 (14)
C3	0.8091 (15)	0.1982 (5)	0.2763 (3)	0.0419 (15)
C4	1.0094 (15)	0.1881 (5)	0.3238 (3)	0.0442 (15)
C5	1.1108 (15)	0.2704 (5)	0.3547 (3)	0.0425 (15)
H5	1.2421	0.2609	0.3864	0.051*
C6	1.0135 (16)	0.3711 (5)	0.3381 (3)	0.0476 (16)
C7	0.8123 (16)	0.3849 (5)	0.2934 (3)	0.0481 (16)
H7	0.7434	0.4511	0.2839	0.058*
C8	0.1902 (16)	0.2605 (6)	0.1331 (3)	0.0562 (19)
H8A	0.0875	0.3264	0.1380	0.067*
H8B	0.0339	0.2066	0.1302	0.067*
C9	0.3671 (15)	0.2630 (6)	0.0799 (3)	0.0480 (17)
C10	0.4684 (18)	0.3549 (7)	0.0600 (3)	0.066 (2)
H10	0.4266	0.4163	0.0786	0.080*
C11	0.635 (2)	0.3571 (9)	0.0117 (4)	0.082 (3)
H11	0.7064	0.4196	−0.0021	0.099*
C12	0.691 (2)	0.2664 (10)	−0.0149 (4)	0.086 (3)
H12	0.8006	0.2675	−0.0473	0.103*
C13	0.594 (2)	0.1762 (9)	0.0043 (4)	0.084 (3)
H13	0.6386	0.1154	−0.0146	0.101*
C14	0.4270 (18)	0.1718 (7)	0.0517 (4)	0.069 (2)
H14	0.3557	0.1087	0.0646	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0795 (6)	0.0510 (5)	0.0758 (6)	0.0131 (4)	0.0027 (4)	0.0117 (4)
Cl1	0.0979 (16)	0.0525 (11)	0.0767 (14)	−0.0047 (10)	−0.0060 (12)	−0.0098 (10)
N1	0.039 (3)	0.066 (4)	0.044 (3)	0.000 (3)	0.003 (3)	0.003 (3)
O1	0.076 (3)	0.047 (3)	0.053 (3)	0.000 (2)	0.001 (2)	−0.002 (2)
C1	0.039 (4)	0.056 (4)	0.045 (4)	0.002 (3)	0.013 (3)	0.009 (3)
C2	0.039 (3)	0.046 (3)	0.040 (4)	−0.001 (3)	0.016 (3)	0.001 (3)
C3	0.042 (4)	0.042 (3)	0.043 (4)	−0.001 (3)	0.016 (3)	0.001 (3)
C4	0.040 (4)	0.049 (4)	0.045 (4)	0.004 (3)	0.019 (3)	0.008 (3)
C5	0.042 (4)	0.047 (3)	0.039 (4)	0.002 (3)	0.008 (3)	0.001 (3)
C6	0.049 (4)	0.048 (4)	0.046 (4)	−0.001 (3)	0.009 (3)	−0.003 (3)
C7	0.053 (4)	0.042 (3)	0.050 (4)	0.005 (3)	0.011 (3)	0.000 (3)
C8	0.035 (4)	0.078 (5)	0.055 (5)	0.000 (3)	−0.002 (3)	0.001 (4)
C9	0.037 (4)	0.068 (4)	0.038 (4)	0.002 (3)	−0.007 (3)	0.002 (3)
C10	0.052 (5)	0.082 (6)	0.065 (5)	0.000 (4)	−0.002 (4)	0.007 (4)
C11	0.059 (5)	0.115 (8)	0.072 (6)	0.000 (5)	−0.003 (5)	0.028 (6)
C12	0.062 (6)	0.144 (10)	0.051 (6)	0.013 (6)	0.005 (4)	0.006 (6)
C13	0.068 (6)	0.113 (8)	0.070 (6)	0.022 (6)	−0.007 (5)	−0.028 (6)
C14	0.055 (5)	0.081 (6)	0.071 (6)	0.004 (4)	−0.010 (4)	−0.010 (5)

Geometric parameters (Å, º) top

Br1—C4	1.890 (6)	C7—H7	0.93
Cl1—C6	1.741 (7)	C8—C9	1.518 (10)
N1—C1	1.267 (9)	C8—H8A	0.97
N1—C8	1.473 (9)	C8—H8B	0.97
O1—C3	1.325 (8)	C9—C10	1.359 (10)
O1—H1	0.82	C9—C14	1.386 (11)
C1—C2	1.465 (9)	C10—C11	1.392 (12)
C1—H1A	0.93	C10—H10	0.93
C2—C7	1.387 (9)	C11—C12	1.360 (14)
C2—C3	1.422 (9)	C11—H11	0.93
C3—C4	1.397 (9)	C12—C13	1.326 (14)
C4—C5	1.353 (9)	C12—H12	0.93
C5—C6	1.416 (9)	C13—C14	1.377 (13)
C5—H5	0.93	C13—H13	0.93
C6—C7	1.355 (9)	C14—H14	0.93

C1—N1—C8	119.5 (6)	N1—C8—H8A	109.7
C3—O1—H1	109.5	C9—C8—H8A	109.7
N1—C1—C2	122.7 (6)	N1—C8—H8B	109.7
N1—C1—H1A	118.7	C9—C8—H8B	109.7
C2—C1—H1A	118.7	H8A—C8—H8B	108.2
C7—C2—C3	120.7 (6)	C10—C9—C14	119.8 (8)
C7—C2—C1	120.6 (6)	C10—C9—C8	119.9 (7)
C3—C2—C1	118.7 (6)	C14—C9—C8	120.3 (7)
O1—C3—C4	120.0 (6)	C9—C10—C11	119.9 (9)
O1—C3—C2	123.2 (6)	C9—C10—H10	120.0
C4—C3—C2	116.9 (6)	C11—C10—H10	120.0
C5—C4—C3	122.7 (6)	C12—C11—C10	118.9 (10)
C5—C4—Br1	117.8 (5)	C12—C11—H11	120.6
C3—C4—Br1	119.4 (5)	C10—C11—H11	120.6
C4—C5—C6	118.9 (6)	C13—C12—C11	121.7 (10)
C4—C5—H5	120.6	C13—C12—H12	119.1
C6—C5—H5	120.6	C11—C12—H12	119.1
C7—C6—C5	120.7 (6)	C12—C13—C14	120.6 (10)
C7—C6—Cl1	120.7 (5)	C12—C13—H13	119.7
C5—C6—Cl1	118.6 (5)	C14—C13—H13	119.7
C6—C7—C2	120.1 (6)	C13—C14—C9	119.0 (9)
C6—C7—H7	120.0	C13—C14—H14	120.5
C2—C7—H7	120.0	C9—C14—H14	120.5
N1—C8—C9	109.6 (5)

C8—N1—C1—C2	−178.6 (6)	C5—C6—C7—C2	−2.7 (10)
N1—C1—C2—C7	175.2 (6)	Cl1—C6—C7—C2	179.2 (5)
N1—C1—C2—C3	−5.7 (9)	C3—C2—C7—C6	0.7 (10)
C7—C2—C3—O1	−178.8 (6)	C1—C2—C7—C6	179.8 (6)
C1—C2—C3—O1	2.1 (9)	C1—N1—C8—C9	102.8 (7)
C7—C2—C3—C4	1.2 (9)	N1—C8—C9—C10	−94.4 (8)
C1—C2—C3—C4	−177.9 (5)	N1—C8—C9—C14	85.3 (8)
O1—C3—C4—C5	178.9 (6)	C14—C9—C10—C11	−0.7 (11)
C2—C3—C4—C5	−1.1 (9)	C8—C9—C10—C11	179.0 (6)
O1—C3—C4—Br1	−3.9 (8)	C9—C10—C11—C12	0.4 (12)
C2—C3—C4—Br1	176.1 (4)	C10—C11—C12—C13	−0.6 (14)
C3—C4—C5—C6	−0.8 (9)	C11—C12—C13—C14	1.0 (14)
Br1—C4—C5—C6	−178.1 (5)	C12—C13—C14—C9	−1.2 (13)
C4—C5—C6—C7	2.7 (10)	C10—C9—C14—C13	1.1 (11)
C4—C5—C6—Cl1	−179.1 (5)	C8—C9—C14—C13	−178.6 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.86	2.590 (7)	147

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁BrClNO
M_r	324.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.3334 (8), 12.8976 (14), 23.892 (2)
β (°)	92.992 (1)
V (Å³)	1333.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.27
Crystal size (mm)	0.40 × 0.37 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.355, 0.676
No. of measured, independent and observed [I > 2σ(I)] reflections	6753, 2325, 1699
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.176, 1.06
No. of reflections	2325
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.47, −0.76

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	1.86	2.590 (7)	147

Acknowledgements

The authors are grateful for research grant No. 08JZ09 from the Phytochemistry Key Laboratory of Shaanxi Province.

References

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