6-Bromo-4-[(3-chloro-4-methyl­phenyl)­imino­meth­yl]-2-meth­oxy-3-nitro­phenol

Zhu, H.; Jiang, H.-H.; Zhu, H.-L.

doi:10.1107/S1600536812023859

organic compounds

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Volume 68| Part 7| July 2012| Page o2023

https://doi.org/10.1107/S1600536812023859

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6-Bromo-4-[(3-chloro-4-methylphenyl)iminomethyl]-2-methoxy-3-nitrophenol

Hui Zhu,^a ^* Hui-Hui Jiang ^a and Hai-Liang Zhu ^a

^aSchool of Life Sciences, Shandong University of Technology, Zibo 255000, People's Republic of China
^*Correspondence e-mail: hailiang_zhu@163.com

(Received 20 March 2012; accepted 25 May 2012; online 13 June 2012)

In the title compound, C₁₅H₁₂BrClN₂O₄, the configuration of the C=N double bond can be described as trans. The two aromatic rings in this Schiff base are nearly coplanar with a dihedral angle between their mean planes of 15.4 (2)°. In the crystal, molecules are linked via O—H⋯N and C—H⋯O interactions.

Related literature

For Schiff bases in coordination chemistry, see: Shao et al. (2004 ) and for their biological activity, see: Desai et al. (2001 ); Venugopal & Jayashree (2008 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₂BrClN₂O₄
M_r = 399.62
Orthorhombic, P b c a
a = 18.288 (2) Å
b = 8.713 (3) Å
c = 19.018 (2) Å
V = 3030.4 (11) Å³
Z = 8
Mo Kα radiation
μ = 2.91 mm⁻¹
T = 296 K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.518, T_max = 0.594
17176 measured reflections
2973 independent reflections
1713 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.149
S = 1.06
2973 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N2ⁱ	0.82	2.15	2.803 (5)	136
C6—H6⋯O2ⁱⁱ	0.93	2.38	3.210 (6)	149
C13—H13⋯O2ⁱⁱ	0.93	2.54	3.295 (6)	138
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 global, I. DOI: https://doi.org/10.1107/S1600536812023859/vm2167sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812023859/vm2167Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812023859/vm2167Isup3.cml

checkCIF report

Comment top

Schiff bases play an important role in the development of coordination chemistry (Shao et al., 2004). Schiff bases have also been shown to exhibit a broad range of biological activities, including antibacterial (Venugopal et al., 2008) and anticancer (Desai et al., 2001) activities. Here we report the synthesis and crystal structure of the title compound (Fig. 1).

The stabilization of the crystal structure is provided by intermolecular hydrogen bonds (Table 1). No π-π interactions are observed in the packing. The compound is weakly twisted, with the dihedral angle between the two benzene rings being 15.4 (2)°. The nitro group makes an angle of 80.7 (3)° withe the best plane through ring C1-C6. All bond lengths are within normal ranges (Allen et al., 1987).

Related literature top

For Schiff bases in coordination chemistry, see: Shao et al. (2004) and for their biological activity, see: Desai et al. (2001); Venugopal & Jayashree (2008). For standard bond lengths, see: Allen et al. (1987);

Experimental top

The title compound was synthetized by reaction between 2-bromo-4-hydroxy-3-methoxy-5-nitro-benzaldehyde (2 mmol) and 3-chloro-4 -methylaniline (2 mmol), dissolved in methanol and mixed together for 4 to 5 h. Large block crystals were precipitated, filtered, washed with ethanol and dried in air (yield 80%).

Structure description top

For Schiff bases in coordination chemistry, see: Shao et al. (2004) and for their biological activity, see: Desai et al. (2001); Venugopal & Jayashree (2008). For standard bond lengths, see: Allen et al. (1987);

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 (I) showing 30% probability displacement ellipsoids.

6-Bromo-4-[(3-chloro-4-methylphenyl)iminomethyl]-2-methoxy-3-nitrophenol top

Crystal data top

C₁₅H₁₂BrClN₂O₄	F(000) = 1600
M_r = 399.62	D_x = 1.752 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2396 reflections
a = 18.288 (2) Å	θ = 2.4–25.2°
b = 8.713 (3) Å	µ = 2.91 mm⁻¹
c = 19.018 (2) Å	T = 296 K
V = 3030.4 (11) Å³	Block, orange
Z = 8	0.26 × 0.22 × 0.20 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2973 independent reflections
Radiation source: fine-focus sealed tube	1713 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
phi and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→22
T_min = 0.518, T_max = 0.594	k = −10→10
17176 measured reflections	l = −23→22

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0664P)²] where P = (F_o² + 2F_c²)/3
2973 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₅H₁₂BrClN₂O₄	V = 3030.4 (11) Å³
M_r = 399.62	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 18.288 (2) Å	µ = 2.91 mm⁻¹
b = 8.713 (3) Å	T = 296 K
c = 19.018 (2) Å	0.26 × 0.22 × 0.20 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2973 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1713 reflections with I > 2σ(I)
T_min = 0.518, T_max = 0.594	R_int = 0.088
17176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.06	Δρ_max = 0.43 e Å⁻³
2973 reflections	Δρ_min = −0.49 e Å⁻³
210 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
Cl1	0.55428 (7)	0.89623 (17)	0.11025 (7)	0.0552 (4)
Br1	1.09270 (3)	0.59794 (7)	0.22933 (3)	0.0560 (3)
N1	0.7871 (2)	0.5746 (5)	0.3498 (2)	0.0453 (11)
N2	0.8252 (2)	0.8332 (4)	0.17064 (18)	0.0337 (9)
O1	0.8983 (2)	0.4633 (5)	0.4246 (2)	0.0673 (12)
O2	1.03988 (18)	0.4585 (4)	0.36915 (17)	0.0490 (9)
H2	1.0785	0.4695	0.3478	0.074*
O3	0.7666 (3)	0.6579 (6)	0.3947 (3)	0.1000 (18)
O4	0.7493 (3)	0.4810 (7)	0.3247 (3)	0.0949 (16)
C1	0.9994 (2)	0.6004 (5)	0.2709 (3)	0.0364 (11)
C2	0.9893 (2)	0.5226 (5)	0.3358 (2)	0.0346 (11)
C3	0.9157 (3)	0.5221 (6)	0.3611 (2)	0.0370 (12)
C4	0.8613 (2)	0.5872 (5)	0.3237 (2)	0.0336 (11)
C5	0.8729 (3)	0.6696 (5)	0.2597 (2)	0.0311 (10)
C6	0.9444 (2)	0.6715 (5)	0.2356 (2)	0.0348 (11)
H6	0.9550	0.7230	0.1940	0.042*
C7	0.8157 (2)	0.7392 (5)	0.2234 (2)	0.0340 (11)
H7	0.7681	0.7177	0.2375	0.041*
C8	0.7679 (2)	0.9012 (5)	0.1301 (2)	0.0321 (11)
C9	0.6953 (2)	0.8724 (5)	0.1399 (2)	0.0338 (11)
H9	0.6798	0.8078	0.1758	0.041*
C10	0.6461 (3)	0.9398 (5)	0.0962 (3)	0.0376 (12)
C11	0.6652 (3)	1.0380 (6)	0.0428 (3)	0.0446 (13)
C12	0.7383 (3)	1.0638 (6)	0.0349 (3)	0.0505 (14)
H12	0.7538	1.1292	−0.0007	0.061*
C13	0.7898 (3)	0.9972 (6)	0.0774 (3)	0.0434 (13)
H13	0.8392	1.0172	0.0704	0.052*
C14	0.6107 (3)	1.1121 (7)	−0.0045 (3)	0.071 (2)
H14A	0.5802	1.1796	0.0225	0.106*
H14B	0.5811	1.0346	−0.0263	0.106*
H14C	0.6358	1.1700	−0.0400	0.106*
C15	0.9170 (4)	0.3327 (8)	0.4458 (3)	0.083 (2)
H15A	0.9309	0.2704	0.4064	0.124*
H15B	0.8767	0.2854	0.4698	0.124*
H15C	0.9576	0.3423	0.4774	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0268 (7)	0.0794 (10)	0.0594 (9)	0.0022 (7)	−0.0050 (6)	−0.0039 (7)
Br1	0.0303 (3)	0.0724 (5)	0.0653 (4)	0.0062 (3)	0.0014 (3)	0.0108 (3)
N1	0.036 (2)	0.057 (3)	0.044 (3)	0.003 (2)	0.000 (2)	0.007 (2)
N2	0.032 (2)	0.035 (2)	0.034 (2)	0.0007 (18)	−0.0099 (17)	−0.0005 (19)
O1	0.053 (3)	0.091 (3)	0.059 (3)	0.021 (2)	0.004 (2)	0.024 (2)
O2	0.0296 (18)	0.070 (2)	0.047 (2)	0.0113 (18)	−0.0033 (16)	0.0053 (18)
O3	0.072 (3)	0.112 (4)	0.116 (4)	−0.001 (3)	0.046 (3)	−0.039 (3)
O4	0.050 (3)	0.112 (4)	0.122 (4)	−0.034 (3)	0.011 (3)	−0.027 (4)
C1	0.022 (2)	0.042 (3)	0.046 (3)	0.000 (2)	−0.002 (2)	−0.005 (2)
C2	0.031 (3)	0.036 (3)	0.036 (3)	0.009 (2)	−0.007 (2)	−0.005 (2)
C3	0.038 (3)	0.044 (3)	0.029 (3)	0.001 (2)	−0.003 (2)	−0.001 (2)
C4	0.024 (2)	0.035 (3)	0.042 (3)	0.004 (2)	−0.003 (2)	−0.009 (2)
C5	0.027 (2)	0.029 (2)	0.037 (3)	0.001 (2)	−0.004 (2)	0.001 (2)
C6	0.030 (3)	0.039 (3)	0.035 (3)	0.003 (2)	−0.002 (2)	0.000 (2)
C7	0.025 (2)	0.036 (3)	0.041 (3)	0.004 (2)	−0.004 (2)	−0.007 (2)
C8	0.026 (2)	0.032 (3)	0.037 (3)	0.004 (2)	−0.004 (2)	−0.004 (2)
C9	0.034 (3)	0.036 (3)	0.031 (2)	0.001 (2)	−0.001 (2)	0.001 (2)
C10	0.025 (2)	0.044 (3)	0.044 (3)	0.003 (2)	−0.005 (2)	−0.009 (2)
C11	0.037 (3)	0.050 (3)	0.047 (3)	0.007 (3)	−0.009 (2)	−0.001 (3)
C12	0.042 (3)	0.053 (4)	0.056 (3)	−0.005 (3)	−0.008 (3)	0.020 (3)
C13	0.036 (3)	0.049 (3)	0.045 (3)	−0.005 (3)	−0.007 (2)	0.005 (3)
C14	0.048 (4)	0.083 (5)	0.080 (5)	0.006 (3)	−0.016 (3)	0.030 (4)
C15	0.111 (6)	0.082 (5)	0.055 (4)	0.013 (4)	0.036 (4)	0.032 (4)

Geometric parameters (Å, º) top

Cl1—C10	1.743 (5)	C6—H6	0.9300
Br1—C1	1.880 (5)	C7—H7	0.9300
N1—O4	1.171 (5)	C8—C9	1.365 (6)
N1—O3	1.182 (6)	C8—C13	1.365 (6)
N1—C4	1.448 (6)	C9—C10	1.358 (6)
N2—C7	1.307 (5)	C9—H9	0.9300
N2—C8	1.429 (5)	C10—C11	1.374 (7)
O1—C15	1.255 (7)	C11—C12	1.362 (7)
O1—C3	1.350 (6)	C11—C14	1.489 (7)
O2—C2	1.253 (5)	C12—C13	1.370 (7)
O2—H2	0.8200	C12—H12	0.9300
C1—C6	1.360 (6)	C13—H13	0.9300
C1—C2	1.420 (7)	C14—H14A	0.9600
C2—C3	1.429 (6)	C14—H14B	0.9600
C3—C4	1.348 (6)	C14—H14C	0.9600
C4—C5	1.429 (6)	C15—H15A	0.9600
C5—C6	1.386 (6)	C15—H15B	0.9600
C5—C7	1.392 (6)	C15—H15C	0.9600

O4—N1—O3	122.3 (5)	C13—C8—N2	115.9 (4)
O4—N1—C4	117.9 (5)	C10—C9—C8	118.8 (4)
O3—N1—C4	119.9 (5)	C10—C9—H9	120.6
C7—N2—C8	125.3 (4)	C8—C9—H9	120.6
C15—O1—C3	124.6 (5)	C9—C10—C11	123.6 (5)
C2—O2—H2	109.5	C9—C10—Cl1	116.8 (4)
C6—C1—C2	123.4 (4)	C11—C10—Cl1	119.6 (4)
C6—C1—Br1	118.0 (4)	C12—C11—C10	115.6 (5)
C2—C1—Br1	118.6 (3)	C12—C11—C14	121.2 (5)
O2—C2—C1	123.8 (4)	C10—C11—C14	123.1 (5)
O2—C2—C3	121.6 (4)	C11—C12—C13	122.7 (5)
C1—C2—C3	114.6 (4)	C11—C12—H12	118.7
O1—C3—C4	117.1 (4)	C13—C12—H12	118.7
O1—C3—C2	121.7 (4)	C8—C13—C12	119.4 (5)
C4—C3—C2	121.1 (4)	C8—C13—H13	120.3
C3—C4—C5	123.4 (4)	C12—C13—H13	120.3
C3—C4—N1	118.7 (4)	C11—C14—H14A	109.5
C5—C4—N1	117.9 (4)	C11—C14—H14B	109.5
C6—C5—C7	122.6 (4)	H14A—C14—H14B	109.5
C6—C5—C4	115.4 (4)	C11—C14—H14C	109.5
C7—C5—C4	122.0 (4)	H14A—C14—H14C	109.5
C1—C6—C5	122.0 (4)	H14B—C14—H14C	109.5
C1—C6—H6	119.0	O1—C15—H15A	109.5
C5—C6—H6	119.0	O1—C15—H15B	109.5
N2—C7—C5	123.7 (4)	H15A—C15—H15B	109.5
N2—C7—H7	118.2	O1—C15—H15C	109.5
C5—C7—H7	118.2	H15A—C15—H15C	109.5
C9—C8—C13	119.8 (4)	H15B—C15—H15C	109.5
C9—C8—N2	124.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N2ⁱ	0.82	2.15	2.803 (5)	136
C6—H6···O2ⁱⁱ	0.93	2.38	3.210 (6)	149
C13—H13···O2ⁱⁱ	0.93	2.54	3.295 (6)	138

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂BrClN₂O₄
M_r	399.62
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	18.288 (2), 8.713 (3), 19.018 (2)
V (Å³)	3030.4 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.91
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.518, 0.594
No. of measured, independent and observed [I > 2σ(I)] reflections	17176, 2973, 1713
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.149, 1.06
No. of reflections	2973
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.49

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
O2—H2···N2ⁱ	0.82	2.15	2.803 (5)	136.1
C6—H6···O2ⁱⁱ	0.93	2.38	3.210 (6)	148.6
C13—H13···O2ⁱⁱ	0.93	2.54	3.295 (6)	137.9

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

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. CSD CrossRef Web of Science Google Scholar
Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desai, S. B., Desai, P. B. & Desai, K. R. (2001). Heterocycl. Commun. 7, 83–90. CrossRef CAS Google Scholar
Shao, S.-C., You, Z.-L., Fan, S.-H., Tang, L.-L., Xiong, Z.-D. & Zhu, H.-L. (2004). Acta Cryst. E60, o2183–o2184. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Venugopal, K. N. & Jayashree, B. S. (2008). Indian J. Pharm. Sci. 70, 88–91. Web of Science PubMed Google Scholar

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