4-Bromo-2-[(E)-(4-chloro­phen­yl)imino­meth­yl]phenol

Ardakani, A.A.; Kia, R.; Kargar, H.; Tahir, M.N.

doi:10.1107/S1600536811004417

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o597

doi:10.1107/S1600536811004417

Open

access

4-Bromo-2-[(E)-(4-chlorophenyl)iminomethyl]phenol

Amir Adabi Ardakani,^a Reza Kia,^b ^* Hadi Kargar ^c and Muhammad Nawaz Tahir ^d ^*

^aIslamic Azad University, Ardakan Branch, Iran, ^bX-ray Crystallography Laboratory, Plasma Physics Research Center, Science and Research Branch, Islamic Azad University, Tehran, Iran, ^cChemistry Department, Payame Noor University, Tehran 19395-4697, I. R. of Iran, and ^dDepartment of Physics, University of Sargodha, Punjab, Pakistan
^*Correspondence e-mail: zsrkk@yahoo.com, rkia@srbiau.ac.ir, dmntahir_uos@yahoo.com

(Received 1 February 2011; accepted 6 February 2011; online 12 February 2011)

In the title compound, C₁₃H₉BrClNO, the dihedral angle between the substituted benzene rings is 43.90 (11)°. Strong intramolecular O—H⋯N hydrogen bonds generate S(6) ring motifs. The crystal structure features short intemolecular Br⋯Br [3.554 (2) Å] and Cl⋯Cl [3.412 (2) Å] contacts. The crystal packing is further stabilized by intermolecular C—H⋯O and C—H⋯π interactions.

Related literature

For standard bond lengths, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For van der Waals radii, see: Bondi (1964 ).

Experimental

Crystal data

C₁₃H₉BrClNO
M_r = 310.57
Monoclinic, P 2₁ /c
a = 27.652 (11) Å
b = 7.011 (3) Å
c = 6.219 (3) Å
β = 96.38 (2)°
V = 1198.2 (8) Å³
Z = 4
Mo Kα radiation
μ = 3.63 mm⁻¹
T = 296 K
0.35 × 0.25 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.363, T_max = 0.502
5719 measured reflections
2170 independent reflections
1718 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.078
S = 1.02
2170 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.87	2.594 (3)	147
C9—H9⋯O1ⁱ	0.93	2.60	3.459 (4)	154
C10—H10⋯Cg1ⁱⁱ	0.93	2.77	3.474 (3)	134
C13—H13⋯Cg1ⁱⁱⁱ	0.03	2.80	3.501 (3)	133
Symmetry codes: (i) x, y, z-1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004417/jh2265sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004417/jh2265Isup2.hkl

checkCIF report

Comment top

Schiff base ligands are one of the most prevalent systems in coordination chemistry. As part of a general study of Schiff bases, we have determined the crystal structure of the title compound.

The asymmetric unit of the title compound, Fig. 1, comprises a potentially bidentate Schiff base ligand. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. The dihedral angle between the substituted benzene rings is 43.90 (11)Å. Strong intramolecular O—H···N hydrogen bonds generate S(6) ring motifs (Bernstein et al., 1995). The remarkable features of the crystal structure is the intemolecular Br···Br [3.554 (2)Å] and Cl···Cl [3.412 (2)Å] contacts which are shorter than the sum of the van der Waals radii of these atoms (Bondi 1964). The crystal packing is further stabilized by the intermolecular C—H···O hydrogen bond (Table 1) and C—H···π interaction [C10—H10···Cg1ⁱⁱ = 3.474 (3)Å, (ii) X, 3/2 - Y, -1/2 + Z; C13—H13···Cg1ⁱⁱⁱ = 3.501 (3)Å, (iii) X, 1/2 - Y, 1/2 + Z, Cg1 is the centroid of the C1–C6 benzene ring].

Related literature top

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For van der Waals radii, see: Bondi et al. (1964).

Experimental top

The title compound was synthesized by adding 5-bromo-salicylaldehyde (2 mmol) to a solution of p-chloroaniline (2 mmol) in ethanol (20 ml). The mixture was refluxed with stirring for half an hour. The resulting light-yellow solution was filtered. Light-yellow single crystals suitable for X-ray diffraction were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering. Intramolecular hydrogen bonds are drawn as dashed lines.
	Fig. 2. The packing diagram of the title compound, viewed down the b-axis forming sheets through the intermolecular Br···Br and C—H···O interactions. The intermolecular interactions are shown as dashed lines.

4-Bromo-2-[(E)-(4-chlorophenyl)iminomethyl]phenol top

Crystal data top

C₁₃H₉BrClNO	F(000) = 616
M_r = 310.57	D_x = 1.722 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2520 reflections
a = 27.652 (11) Å	θ = 2.5–27.5°
b = 7.011 (3) Å	µ = 3.63 mm⁻¹
c = 6.219 (3) Å	T = 296 K
β = 96.38 (2)°	Prism, light-yellow
V = 1198.2 (8) Å³	0.35 × 0.25 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2170 independent reflections
Radiation source: fine-focus sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −28→33
T_min = 0.363, T_max = 0.502	k = −8→5
5719 measured reflections	l = −7→6

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0399P)² + 0.3051P] where P = (F_o² + 2F_c²)/3
2170 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₃H₉BrClNO	V = 1198.2 (8) Å³
M_r = 310.57	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 27.652 (11) Å	µ = 3.63 mm⁻¹
b = 7.011 (3) Å	T = 296 K
c = 6.219 (3) Å	0.35 × 0.25 × 0.22 mm
β = 96.38 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2170 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1718 reflections with I > 2σ(I)
T_min = 0.363, T_max = 0.502	R_int = 0.026
5719 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.02	Δρ_max = 0.39 e Å⁻³
2170 reflections	Δρ_min = −0.35 e Å⁻³
155 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.456428 (11)	0.43271 (5)	0.67549 (5)	0.05153 (14)
Cl1	0.03796 (3)	0.54095 (14)	0.23081 (16)	0.0684 (3)
O1	0.27742 (7)	0.5674 (3)	1.1170 (3)	0.0444 (5)
H1	0.2529	0.5423	1.0354	0.067*
N1	0.22712 (8)	0.4746 (3)	0.7551 (3)	0.0313 (5)
C1	0.31315 (10)	0.4668 (3)	0.7991 (4)	0.0289 (6)
C2	0.31691 (10)	0.5350 (3)	1.0152 (4)	0.0309 (6)
C3	0.36211 (11)	0.5707 (3)	1.1235 (4)	0.0361 (6)
H3	0.3647	0.6166	1.2646	0.043*
C4	0.40322 (11)	0.5392 (3)	1.0256 (4)	0.0363 (6)
H4	0.4336	0.5642	1.1000	0.044*
C5	0.39973 (10)	0.4695 (3)	0.8134 (4)	0.0331 (6)
C6	0.35529 (10)	0.4331 (3)	0.7031 (4)	0.0304 (6)
H6	0.3532	0.3855	0.5628	0.036*
C7	0.26674 (10)	0.4453 (3)	0.6737 (4)	0.0311 (6)
H7	0.2655	0.4091	0.5294	0.037*
C8	0.18255 (10)	0.4827 (3)	0.6229 (4)	0.0298 (6)
C9	0.17902 (10)	0.5621 (3)	0.4151 (4)	0.0332 (6)
H9	0.2069	0.6033	0.3578	0.040*
C10	0.13425 (11)	0.5790 (3)	0.2961 (4)	0.0365 (6)
H10	0.1315	0.6315	0.1579	0.044*
C11	0.09378 (11)	0.5175 (4)	0.3836 (5)	0.0390 (7)
C12	0.09647 (11)	0.4396 (3)	0.5890 (5)	0.0405 (7)
H12	0.0685	0.3987	0.6455	0.049*
C13	0.14112 (10)	0.4237 (3)	0.7077 (4)	0.0334 (6)
H13	0.1434	0.3727	0.8465	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0284 (2)	0.0679 (2)	0.0599 (2)	−0.00058 (15)	0.01204 (13)	−0.00234 (15)
Cl1	0.0355 (5)	0.0899 (7)	0.0749 (6)	0.0049 (5)	−0.0157 (4)	0.0006 (5)
O1	0.0349 (12)	0.0649 (13)	0.0343 (10)	0.0008 (10)	0.0085 (8)	−0.0095 (9)
N1	0.0270 (13)	0.0334 (11)	0.0336 (11)	−0.0016 (10)	0.0041 (9)	0.0012 (9)
C1	0.0319 (16)	0.0250 (12)	0.0299 (13)	0.0014 (11)	0.0035 (10)	0.0002 (10)
C2	0.0323 (16)	0.0308 (13)	0.0305 (13)	0.0023 (12)	0.0080 (11)	0.0014 (11)
C3	0.0433 (18)	0.0353 (14)	0.0284 (13)	−0.0017 (13)	−0.0015 (11)	−0.0030 (11)
C4	0.0323 (17)	0.0362 (14)	0.0386 (14)	−0.0030 (12)	−0.0045 (12)	0.0012 (11)
C5	0.0273 (16)	0.0307 (13)	0.0417 (14)	0.0010 (11)	0.0055 (11)	0.0044 (11)
C6	0.0331 (16)	0.0297 (13)	0.0285 (12)	0.0022 (12)	0.0034 (10)	−0.0002 (10)
C7	0.0343 (16)	0.0293 (13)	0.0300 (12)	−0.0008 (11)	0.0043 (11)	−0.0025 (10)
C8	0.0314 (16)	0.0249 (12)	0.0336 (13)	0.0012 (11)	0.0057 (11)	−0.0015 (10)
C9	0.0321 (16)	0.0346 (14)	0.0338 (13)	−0.0017 (12)	0.0083 (11)	0.0022 (11)
C10	0.0381 (18)	0.0351 (14)	0.0358 (14)	0.0041 (12)	0.0014 (12)	0.0011 (11)
C11	0.0291 (17)	0.0362 (14)	0.0502 (16)	0.0038 (13)	−0.0029 (13)	−0.0057 (13)
C12	0.0298 (17)	0.0396 (15)	0.0531 (17)	−0.0042 (13)	0.0095 (13)	−0.0017 (13)
C13	0.0308 (16)	0.0348 (14)	0.0358 (13)	−0.0013 (12)	0.0087 (11)	0.0036 (11)

Geometric parameters (Å, º) top

Br1—C5	1.886 (3)	C5—C6	1.363 (4)
Cl1—C11	1.728 (3)	C6—H6	0.9300
O1—C2	1.341 (3)	C7—H7	0.9300
O1—H1	0.8200	C8—C13	1.377 (4)
N1—C7	1.273 (3)	C8—C9	1.400 (3)
N1—C8	1.405 (3)	C9—C10	1.375 (4)
C1—C6	1.387 (4)	C9—H9	0.9300
C1—C2	1.420 (3)	C10—C11	1.367 (4)
C1—C7	1.434 (4)	C10—H10	0.9300
C2—C3	1.375 (4)	C11—C12	1.384 (4)
C3—C4	1.366 (4)	C12—C13	1.371 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.401 (4)	C13—H13	0.9300
C4—H4	0.9300

C2—O1—H1	109.5	N1—C7—H7	119.2
C7—N1—C8	120.8 (2)	C1—C7—H7	119.2
C6—C1—C2	119.2 (2)	C13—C8—C9	119.8 (3)
C6—C1—C7	119.5 (2)	C13—C8—N1	118.5 (2)
C2—C1—C7	121.1 (2)	C9—C8—N1	121.5 (2)
O1—C2—C3	118.8 (2)	C10—C9—C8	119.8 (3)
O1—C2—C1	121.7 (2)	C10—C9—H9	120.1
C3—C2—C1	119.5 (3)	C8—C9—H9	120.1
C4—C3—C2	120.6 (2)	C11—C10—C9	119.1 (3)
C4—C3—H3	119.7	C11—C10—H10	120.4
C2—C3—H3	119.7	C9—C10—H10	120.4
C3—C4—C5	120.2 (3)	C10—C11—C12	122.0 (3)
C3—C4—H4	119.9	C10—C11—Cl1	118.1 (2)
C5—C4—H4	119.9	C12—C11—Cl1	119.9 (2)
C6—C5—C4	120.2 (3)	C13—C12—C11	118.8 (3)
C6—C5—Br1	119.6 (2)	C13—C12—H12	120.6
C4—C5—Br1	120.2 (2)	C11—C12—H12	120.6
C5—C6—C1	120.3 (2)	C12—C13—C8	120.5 (2)
C5—C6—H6	119.8	C12—C13—H13	119.8
C1—C6—H6	119.8	C8—C13—H13	119.8
N1—C7—C1	121.7 (2)

C6—C1—C2—O1	−179.0 (2)	C6—C1—C7—N1	180.0 (2)
C7—C1—C2—O1	5.5 (4)	C2—C1—C7—N1	−4.6 (4)
C6—C1—C2—C3	1.5 (3)	C7—N1—C8—C13	149.2 (2)
C7—C1—C2—C3	−173.9 (2)	C7—N1—C8—C9	−35.6 (3)
O1—C2—C3—C4	179.9 (2)	C13—C8—C9—C10	−0.6 (4)
C1—C2—C3—C4	−0.7 (4)	N1—C8—C9—C10	−175.7 (2)
C2—C3—C4—C5	−0.2 (4)	C8—C9—C10—C11	0.0 (4)
C3—C4—C5—C6	0.2 (4)	C9—C10—C11—C12	0.3 (4)
C3—C4—C5—Br1	178.26 (19)	C9—C10—C11—Cl1	179.82 (19)
C4—C5—C6—C1	0.7 (4)	C10—C11—C12—C13	0.0 (4)
Br1—C5—C6—C1	−177.37 (17)	Cl1—C11—C12—C13	−179.53 (19)
C2—C1—C6—C5	−1.6 (4)	C11—C12—C13—C8	−0.6 (4)
C7—C1—C6—C5	174.0 (2)	C9—C8—C13—C12	0.9 (4)
C8—N1—C7—C1	169.8 (2)	N1—C8—C13—C12	176.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.594 (3)	147
C9—H9···O1ⁱ	0.93	2.60	3.459 (4)	154
C10—H10···Cg1ⁱⁱ	0.93	2.77	3.474 (3)	134
C13—H13···Cg1ⁱⁱⁱ	0.03	2.80	3.501 (3)	133

Symmetry codes: (i) x, y, z−1; (ii) x, −y+3/2, z−1/2; (iii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉BrClNO
M_r	310.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	27.652 (11), 7.011 (3), 6.219 (3)
β (°)	96.38 (2)
V (Å³)	1198.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.63
Crystal size (mm)	0.35 × 0.25 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.363, 0.502
No. of measured, independent and observed [I > 2σ(I)] reflections	5719, 2170, 1718
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.02
No. of reflections	2170
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.35

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.87	2.594 (3)	147
C9—H9···O1ⁱ	0.93	2.60	3.459 (4)	153.8
C10—H10···Cg1ⁱⁱ	0.93	2.77	3.474 (3)	134
C13—H13···Cg1ⁱⁱⁱ	0.03	2.80	3.501 (3)	133

Symmetry codes: (i) x, y, z−1; (ii) x, −y+3/2, z−1/2; (iii) x, −y+1/2, z+1/2.

Acknowledgements

AAA thanks the Islamic Azad University, Ardakan Branch, for the research facilities (this paper was extracted from a research project). HK thanks the PNU for financial support. RK thanks the Science and Research Branch, Islamic Azad University, Tehran. MNT thanks Sargodha University for the research facilities.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o597

doi:10.1107/S1600536811004417

Open

access