(E)-2-[1-(3-Amino-4-chloro­phenyl­imino)eth­yl]-4-bromo­phenol

Bahron, H.; Bakar, S.N.A.; Kassim, K.; Yeap, C.S.; Fun, H.-K.

doi:10.1107/S1600536810009773

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o883

doi:10.1107/S1600536810009773

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(E)-2-[1-(3-Amino-4-chlorophenylimino)ethyl]-4-bromophenol

Hadariah Bahron,^a Siti Najihah Abu Bakar,^a Karimah Kassim,^a Chin Sing Yeap ^b ‡ and Hoong-Kun Fun ^b ^*§

^aFaculty of Applied Sciences, Universiti Teknologi MARA, 40450, Shah Alam, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 10 March 2010; accepted 16 March 2010; online 20 March 2010)

The title Schiff base compound, C₁₄H₁₂BrClN₂O, exists in an E configuration with respect to the central C=N double bond. The amino group adopts a pyramidal configuration. The dihedral angle between the two benzene rings is 76.88 (10)° and an intramolecular O—H⋯N hydrogen bond forms a six-membered ring, generating an S(6) ring motif. In the crystal structure, molecules are linked into chains along [010] via N—H⋯O hydrogen bonds. The presence of π–π interactions [centroid–centroid distance = 3.6244 (12) Å] further stabilizes the crystal structure.

Related literature

For the biological activity and corrosion inhibition properties of Schiff base derivatives, see: Azam et al. (2007 ); Sauri et al. (2009 ). For a related structure, see: Yamin et al. (2009 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₂BrClN₂O
M_r = 339.62
Monoclinic, P 2₁ /c
a = 10.2469 (1) Å
b = 8.7672 (1) Å
c = 15.7180 (2) Å
β = 107.065 (1)°
V = 1349.88 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.24 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.509, T_max = 0.726
14782 measured reflections
3925 independent reflections
2420 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.077
S = 1.00
3925 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N1	0.86 (3)	1.74 (3)	2.533 (2)	151 (3)
N2—H1N2⋯O1ⁱ	0.82 (3)	2.33 (3)	3.129 (3)	163 (2)
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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/S1600536810009773/tk2641sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009773/tk2641Isup2.hkl

checkCIF report

Comment top

Schiff bases have been studied extensively due to their intriguing biological activities, such as antimicrobial (Azam et al., 2007), and chemical properties as well as corrosion inhibition (Sauri et al., 2009). The structure of a Schiff base synthesized from 1,3-diamino-4-chlorobenzene and 3-methoxysalicylaldehyde in 1:2 ratio has been reported by Yamin et al. (2009). The present Schiff base compound, (I), is also derived from 1,3-diamino-4-chlorobenzene but from an analogous reaction with 5-bromo-2-hydroxyacetophenone.

Compound, (I), exists in an E configuration with respect to the central C7═N1 double bond (Fig. 1). The dihedral angle between the two benzene rings is 76.88 (10)°. The amino group (N2) adopts a pyramidal configuration. An intramolecular O1—H1O1···N1 hydrogen bond forms a six-membered ring, generating an S(6) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are linked into one-dimensional chains along [010] via intermolecular N2—H1N2···O1 hydrogen bonds (Fig. 2, Table 1). The Cg1···Cg2 interaction of 3.6244 (12) Å; x, 5/2-y, 1/2+z, further stabilizes the crystal structure (Cg1 and Cg2 are centroids of benzene rings C8–C13 and C1–C6, respectively).

Related literature top

For the biological activity and chemical properties of Schiff base derivatives, see: Azam et al. (2007); Sauri et al. (2009). For a related structure, see: Yamin et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

Compound (I) was synthesized by heating 1,3-diamino-4-chlorobenzene (0.3565 g, 2.5 mmol) with 5-bromo-2-hydroxyacetophenone (0.998 g, 5 mmol) in ethanol for 24 h. The solvent was then evaporated in-vacuo and the oily product was recrystallized from acetone to afford yellow single crystals. Yield 12%. Melting point 448-452 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 molecular structure of (I) with 50% probability ellipsoids for non-H atoms. An intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. A view down the a axis of the unit cell of (I) showing molecules linked into one-dimensional chains along [010]. Intermolecular hydrogen bonds are shown as dashed lines.

(E)-2-[1-(3-Amino-4-chlorophenylimino)ethyl]-4-bromophenol top

Crystal data top

C₁₄H₁₂BrClN₂O	F(000) = 680
M_r = 339.62	D_x = 1.671 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4343 reflections
a = 10.2469 (1) Å	θ = 2.7–28.5°
b = 8.7672 (1) Å	µ = 3.24 mm⁻¹
c = 15.7180 (2) Å	T = 296 K
β = 107.065 (1)°	Block, yellow
V = 1349.88 (3) Å³	0.24 × 0.22 × 0.11 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3925 independent reflections
Radiation source: fine-focus sealed tube	2420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 30.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.509, T_max = 0.726	k = −12→9
14782 measured reflections	l = −22→21

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0299P)² + 0.2742P] where P = (F_o² + 2F_c²)/3
3925 reflections	(Δ/σ)_max = 0.001
185 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₁₂BrClN₂O	V = 1349.88 (3) Å³
M_r = 339.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.2469 (1) Å	µ = 3.24 mm⁻¹
b = 8.7672 (1) Å	T = 296 K
c = 15.7180 (2) Å	0.24 × 0.22 × 0.11 mm
β = 107.065 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3925 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2420 reflections with I > 2σ(I)
T_min = 0.509, T_max = 0.726	R_int = 0.029
14782 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.28 e Å⁻³
3925 reflections	Δρ_min = −0.27 e Å⁻³
185 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 > 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	0.82408 (3)	0.92283 (3)	0.233924 (15)	0.05982 (11)
Cl1	0.55171 (6)	1.10458 (7)	0.92352 (4)	0.05352 (17)
O1	0.92270 (16)	1.31628 (18)	0.55948 (10)	0.0499 (4)
N1	0.76555 (17)	1.1434 (2)	0.61354 (10)	0.0391 (4)
N2	0.7688 (2)	0.9064 (2)	0.89348 (14)	0.0503 (5)
C1	0.9012 (2)	1.2211 (2)	0.48934 (12)	0.0361 (5)
C2	0.9613 (2)	1.2577 (3)	0.42328 (13)	0.0415 (5)
H2A	1.0168	1.3435	0.4298	0.050*
C3	0.9398 (2)	1.1686 (3)	0.34850 (13)	0.0411 (5)
H3A	0.9795	1.1944	0.3043	0.049*
C4	0.8588 (2)	1.0407 (2)	0.33972 (12)	0.0376 (5)
C5	0.7997 (2)	1.0004 (2)	0.40428 (13)	0.0377 (5)
H5A	0.7462	0.9130	0.3971	0.045*
C6	0.81908 (19)	1.0898 (2)	0.48087 (12)	0.0325 (4)
C7	0.75211 (19)	1.0490 (2)	0.54920 (13)	0.0341 (5)
C8	0.7052 (2)	1.1213 (2)	0.68396 (12)	0.0349 (5)
C9	0.7605 (2)	1.0181 (2)	0.75146 (13)	0.0361 (5)
H9A	0.8302	0.9534	0.7471	0.043*
C10	0.71348 (19)	1.0095 (2)	0.82588 (12)	0.0343 (5)
C11	0.6078 (2)	1.1068 (2)	0.82884 (13)	0.0353 (5)
C12	0.5507 (2)	1.2078 (3)	0.76140 (14)	0.0457 (5)
H12A	0.4790	1.2703	0.7648	0.055*
C13	0.6000 (2)	1.2166 (3)	0.68838 (14)	0.0442 (5)
H13A	0.5626	1.2857	0.6429	0.053*
C14	0.6714 (2)	0.9042 (2)	0.53932 (15)	0.0497 (6)
H14A	0.6292	0.8973	0.5862	0.075*
H14B	0.7311	0.8186	0.5426	0.075*
H14C	0.6022	0.9040	0.4828	0.075*
H1O1	0.875 (3)	1.280 (3)	0.5918 (17)	0.090 (10)*
H1N2	0.845 (3)	0.875 (3)	0.8945 (15)	0.056 (8)*
H2N2	0.760 (3)	0.933 (3)	0.9416 (18)	0.068 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0789 (2)	0.0630 (2)	0.04600 (15)	0.00123 (13)	0.03142 (13)	−0.01291 (12)
Cl1	0.0612 (4)	0.0630 (4)	0.0472 (3)	0.0015 (3)	0.0328 (3)	−0.0020 (3)
O1	0.0632 (10)	0.0497 (10)	0.0423 (9)	−0.0224 (8)	0.0241 (8)	−0.0097 (7)
N1	0.0511 (11)	0.0378 (10)	0.0321 (9)	−0.0088 (8)	0.0180 (8)	−0.0014 (8)
N2	0.0585 (14)	0.0534 (14)	0.0435 (12)	0.0162 (11)	0.0222 (11)	0.0160 (10)
C1	0.0383 (11)	0.0381 (13)	0.0314 (10)	−0.0005 (9)	0.0095 (9)	0.0032 (9)
C2	0.0408 (12)	0.0428 (13)	0.0425 (12)	−0.0045 (10)	0.0149 (10)	0.0046 (10)
C3	0.0418 (12)	0.0469 (14)	0.0400 (11)	0.0060 (11)	0.0206 (10)	0.0106 (10)
C4	0.0426 (11)	0.0396 (13)	0.0320 (10)	0.0090 (10)	0.0131 (9)	0.0022 (9)
C5	0.0435 (12)	0.0327 (12)	0.0391 (11)	0.0000 (10)	0.0157 (10)	0.0005 (9)
C6	0.0348 (10)	0.0327 (12)	0.0306 (10)	0.0014 (9)	0.0106 (8)	0.0037 (9)
C7	0.0378 (11)	0.0323 (12)	0.0328 (10)	−0.0004 (9)	0.0113 (9)	0.0033 (9)
C8	0.0420 (11)	0.0335 (12)	0.0303 (10)	−0.0072 (9)	0.0123 (9)	−0.0034 (9)
C9	0.0398 (11)	0.0340 (12)	0.0381 (11)	0.0030 (9)	0.0169 (9)	−0.0008 (9)
C10	0.0388 (11)	0.0318 (12)	0.0317 (10)	−0.0037 (9)	0.0094 (9)	0.0002 (9)
C11	0.0401 (11)	0.0370 (12)	0.0329 (10)	−0.0029 (9)	0.0173 (9)	−0.0036 (9)
C12	0.0457 (12)	0.0461 (14)	0.0489 (13)	0.0087 (11)	0.0195 (11)	0.0025 (11)
C13	0.0499 (13)	0.0445 (14)	0.0377 (11)	0.0061 (11)	0.0121 (10)	0.0082 (10)
C14	0.0631 (15)	0.0461 (15)	0.0480 (13)	−0.0175 (11)	0.0288 (11)	−0.0101 (11)

Geometric parameters (Å, º) top

Br1—C4	1.900 (2)	C5—C6	1.401 (3)
Cl1—C11	1.7458 (18)	C5—H5A	0.9300
O1—C1	1.348 (2)	C6—C7	1.478 (2)
O1—H1O1	0.86 (3)	C7—C14	1.498 (3)
N1—C7	1.282 (2)	C8—C13	1.382 (3)
N1—C8	1.431 (2)	C8—C9	1.383 (3)
N2—C10	1.384 (3)	C9—C10	1.392 (2)
N2—H1N2	0.82 (3)	C9—H9A	0.9300
N2—H2N2	0.82 (3)	C10—C11	1.390 (3)
C1—C2	1.392 (3)	C11—C12	1.373 (3)
C1—C6	1.409 (3)	C12—C13	1.385 (3)
C2—C3	1.374 (3)	C12—H12A	0.9300
C2—H2A	0.9300	C13—H13A	0.9300
C3—C4	1.378 (3)	C14—H14A	0.9600
C3—H3A	0.9300	C14—H14B	0.9600
C4—C5	1.372 (3)	C14—H14C	0.9600

C1—O1—H1O1	105.6 (19)	C6—C7—C14	119.31 (17)
C7—N1—C8	123.50 (17)	C13—C8—C9	120.47 (17)
C10—N2—H1N2	114.0 (17)	C13—C8—N1	118.56 (18)
C10—N2—H2N2	112.9 (18)	C9—C8—N1	120.61 (18)
H1N2—N2—H2N2	116 (2)	C8—C9—C10	120.98 (18)
O1—C1—C2	117.72 (19)	C8—C9—H9A	119.5
O1—C1—C6	122.22 (17)	C10—C9—H9A	119.5
C2—C1—C6	120.05 (19)	N2—C10—C11	121.52 (18)
C3—C2—C1	120.8 (2)	N2—C10—C9	121.06 (19)
C3—C2—H2A	119.6	C11—C10—C9	117.42 (18)
C1—C2—H2A	119.6	C12—C11—C10	121.97 (17)
C2—C3—C4	119.29 (18)	C12—C11—Cl1	119.54 (15)
C2—C3—H3A	120.4	C10—C11—Cl1	118.44 (15)
C4—C3—H3A	120.4	C11—C12—C13	119.95 (19)
C5—C4—C3	121.26 (19)	C11—C12—H12A	120.0
C5—C4—Br1	119.84 (16)	C13—C12—H12A	120.0
C3—C4—Br1	118.87 (14)	C8—C13—C12	119.2 (2)
C4—C5—C6	120.66 (19)	C8—C13—H13A	120.4
C4—C5—H5A	119.7	C12—C13—H13A	120.4
C6—C5—H5A	119.7	C7—C14—H14A	109.5
C5—C6—C1	117.94 (17)	C7—C14—H14B	109.5
C5—C6—C7	120.68 (18)	H14A—C14—H14B	109.5
C1—C6—C7	121.36 (17)	C7—C14—H14C	109.5
N1—C7—C6	116.84 (17)	H14A—C14—H14C	109.5
N1—C7—C14	123.84 (17)	H14B—C14—H14C	109.5

O1—C1—C2—C3	−177.75 (18)	C5—C6—C7—C14	4.6 (3)
C6—C1—C2—C3	1.2 (3)	C1—C6—C7—C14	−177.06 (19)
C1—C2—C3—C4	−0.8 (3)	C7—N1—C8—C13	−110.9 (2)
C2—C3—C4—C5	−0.2 (3)	C7—N1—C8—C9	76.0 (3)
C2—C3—C4—Br1	177.57 (15)	C13—C8—C9—C10	−1.2 (3)
C3—C4—C5—C6	0.6 (3)	N1—C8—C9—C10	171.82 (18)
Br1—C4—C5—C6	−177.08 (14)	C8—C9—C10—N2	−180.0 (2)
C4—C5—C6—C1	−0.2 (3)	C8—C9—C10—C11	1.0 (3)
C4—C5—C6—C7	178.20 (18)	N2—C10—C11—C12	−178.9 (2)
O1—C1—C6—C5	178.19 (18)	C9—C10—C11—C12	0.2 (3)
C2—C1—C6—C5	−0.7 (3)	N2—C10—C11—Cl1	3.7 (3)
O1—C1—C6—C7	−0.2 (3)	C9—C10—C11—Cl1	−177.24 (15)
C2—C1—C6—C7	−179.09 (18)	C10—C11—C12—C13	−1.1 (3)
C8—N1—C7—C6	179.02 (17)	Cl1—C11—C12—C13	176.27 (17)
C8—N1—C7—C14	0.2 (3)	C9—C8—C13—C12	0.2 (3)
C5—C6—C7—N1	−174.25 (18)	N1—C8—C13—C12	−172.91 (19)
C1—C6—C7—N1	4.1 (3)	C11—C12—C13—C8	0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.86 (3)	1.74 (3)	2.533 (2)	151 (3)
N2—H1N2···O1ⁱ	0.82 (3)	2.33 (3)	3.129 (3)	163 (2)

Symmetry code: (i) −x+2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂BrClN₂O
M_r	339.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.2469 (1), 8.7672 (1), 15.7180 (2)
β (°)	107.065 (1)
V (Å³)	1349.88 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.24
Crystal size (mm)	0.24 × 0.22 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.509, 0.726
No. of measured, independent and observed [I > 2σ(I)] reflections	14782, 3925, 2420
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.077, 1.00
No. of reflections	3925
No. of parameters	185
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.27

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.86 (3)	1.74 (3)	2.533 (2)	151 (3)
N2—H1N2···O1ⁱ	0.82 (3)	2.33 (3)	3.129 (3)	163 (2)

Symmetry code: (i) −x+2, y−1/2, −z+3/2.

Footnotes

‡Thomson Reuters ResearcherID: A-5523-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HB, SNAB and KK wish to thank both Universiti Teknologi MARA and Universiti Sains Malaysia (USM) for research facilities, and the Malaysian Ministry of Higher Education for the research grant FRGS UiTM 5/3/FST/(12/2008). HKF and CSY thank USM for the Research University Golden Goose grant (1001/PFIZIK/811012). CSY also thanks USM for the award of a USM Fellowship.

References

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