4-[(E)-(3-Chloro-4-methyl­phen­yl)imino­meth­yl]-2-methoxy-3-nitro­phenyl acetate

Su, D.-C.; Wang, F.-T.; Mao, C.-G.; Qian, S.-S.

doi:10.1107/S1600536811055590

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o303

doi:10.1107/S1600536811055590

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4-[(E)-(3-Chloro-4-methylphenyl)iminomethyl]-2-methoxy-3-nitrophenyl acetate

Deng-Cheng Su,^a Feng-Ting Wang,^a Cheng-Gong Mao ^a and Shao-Song Qian ^a ^*

^aSchool of Life Sciences, Shandong University of Technology, ZiBo 255049, People's Republic of China
^*Correspondence e-mail: njuqss@yahoo.com.cn

(Received 16 December 2011; accepted 25 December 2011; online 7 January 2012)

The title compound, C₁₇H₁₅ClN₂O₅, displays a trans-configuration with respect to the C=N double bond. The molecule is twisted, the dihedral angle between the mean planes of the two benzene rings being 18.70 (12)°. The nitro, methoxy and acetyl groups are oriented at 80.70 (11), 35.2 (2) and 72.35 (10)°, respectively, to the benzene ring to which they are bonded. The crystal structure is stabilized by weak C—H⋯O hydrogen-bonding contacts.

Related literature

For background to Schiff bases in coordination chemistry, see: Bhatia et al. (1981 ); Costamagna et al. (1992 ). For a related structure, see: Qian & Liu (2010 ).

Experimental

Crystal data

C₁₇H₁₅ClN₂O₅
M_r = 362.76
Triclinic, $[P \overline 1]$
a = 7.035 (6) Å
b = 7.672 (6) Å
c = 17.272 (14) Å
α = 83.477 (8)°
β = 84.994 (8)°
γ = 66.697 (7)°
V = 849.7 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.26 × 0.23 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.936, T_max = 0.948
5579 measured reflections
3083 independent reflections
2207 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.122
S = 1.05
3083 reflections
229 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1ⁱ	0.93	2.58	3.431 (3)	153
Symmetry code: (i) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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: 10.1107/S1600536811055590/pv2498sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055590/pv2498Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811055590/pv2498Isup3.cml

checkCIF report

Comment top

Schiff bases play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures (Costamagna et al., 1992; Bhatia et al., 1981). As an extension of work on the structural characterization of Schiff base compounds, we report the synthesis and crystal structure of the title compound in this article.

The title compound (Fig. 1) assumes an E conformation about the C═N double bond. The molecule is twisted, with the dihedral angle between the two benzene rings being 18.70 (12)°. The nitro (N2/O1/O2), methoxy (O3/C15) and ethanone (O4/O5/C16/C17) groups are oriented with respect to the benzene ring (C8–C13) to which they are bonded, at 80.70 (11), 35.2 (2) and 72.35 (10) °, respectively. The crystal structure is stabilized by π-π interactions [centroid-centroid distance = 3.886 (4) Å ] and weak C12—H12···O1 hydrogen bonding contacts.

The bond lengths and bond angles in the title compound are comparable to the corresponding bond lengths and bond angles observed in a closely related compound (Qian & Liu, 2010).

Related literature top

For background to Schiff basesin coordination chemistry, see: Bhatia et al. (1981); Costamagna et al. (1992). For a related structure, see: Qian & Liu (2010).

Experimental top

4-Formyl-2-methoxy-3-nitrophenyl acetate (0.0995 g) and 3-chloro-4-methylaniline (0.0706 g) were dissolved in methanol (20 mL). The mixture was stirred at room temperature for 45 mins to give a clear solution. The solution was allowed to stand in the air for 3 days. Yellow block-shaped single crystals of the title compound suitable for X-ray diffraction analysis were obtained at the bottom of the vessel.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing diagram for the title compound; hydrogen-bonding interactions are represented by dashed lines.

4-[(E)-(3-Chloro-4-methylphenyl)iminomethyl]-2-methoxy-3-nitrophenyl acetate top

Crystal data top

C₁₇H₁₅ClN₂O₅	Z = 2
M_r = 362.76	F(000) = 376
Triclinic, P1	D_x = 1.418 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.035 (6) Å	Cell parameters from 3083 reflections
b = 7.672 (6) Å	θ = 2.4–25.5°
c = 17.272 (14) Å	µ = 0.26 mm⁻¹
α = 83.477 (8)°	T = 296 K
β = 84.994 (8)°	Block, yellow
γ = 66.697 (7)°	0.26 × 0.23 × 0.21 mm
V = 849.7 (12) Å³

Data collection top

Bruker APEXII CCD diffractometer	3083 independent reflections
Radiation source: fine-focus sealed tube	2207 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
T_min = 0.936, T_max = 0.948	k = −9→9
5579 measured reflections	l = −20→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0433P)² + 0.4254P] where P = (F_o² + 2F_c²)/3
3083 reflections	(Δ/σ)_max < 0.001
229 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₇H₁₅ClN₂O₅	γ = 66.697 (7)°
M_r = 362.76	V = 849.7 (12) Å³
Triclinic, P1	Z = 2
a = 7.035 (6) Å	Mo Kα radiation
b = 7.672 (6) Å	µ = 0.26 mm⁻¹
c = 17.272 (14) Å	T = 296 K
α = 83.477 (8)°	0.26 × 0.23 × 0.21 mm
β = 84.994 (8)°

Data collection top

Bruker APEXII CCD diffractometer	3083 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2207 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.948	R_int = 0.022
5579 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.05	Δρ_max = 0.17 e Å⁻³
3083 reflections	Δρ_min = −0.23 e Å⁻³
229 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
Cl1	−0.50222 (11)	1.23475 (11)	0.05852 (6)	0.0880 (3)
O1	−0.3219 (3)	0.5157 (3)	0.34263 (13)	0.0728 (6)
O2	−0.3928 (3)	0.4212 (3)	0.23925 (14)	0.0733 (6)
O3	−0.2466 (2)	0.0650 (2)	0.34480 (11)	0.0563 (5)
O4	0.1492 (2)	−0.2520 (2)	0.35298 (10)	0.0472 (4)
O5	0.2885 (4)	−0.2451 (3)	0.46343 (13)	0.0891 (8)
N1	−0.0690 (3)	0.6082 (3)	0.20244 (12)	0.0450 (5)
N2	−0.2784 (3)	0.4109 (3)	0.28994 (14)	0.0490 (5)
C1	−0.2521 (3)	0.9075 (3)	0.13350 (15)	0.0491 (6)
H1	−0.3684	0.8771	0.1395	0.059*
C2	−0.2654 (4)	1.0797 (3)	0.09522 (15)	0.0491 (6)
C3	−0.0985 (4)	1.1342 (3)	0.08453 (14)	0.0459 (6)
C4	0.0867 (4)	1.0021 (4)	0.11302 (15)	0.0510 (6)
H4	0.2035	1.0317	0.1061	0.061*
C5	0.1053 (4)	0.8288 (3)	0.15121 (15)	0.0472 (6)
H5	0.2328	0.7443	0.1692	0.057*
C6	−0.0665 (3)	0.7799 (3)	0.16295 (13)	0.0405 (5)
C7	0.0954 (3)	0.4730 (3)	0.22155 (15)	0.0469 (6)
H7	0.2197	0.4885	0.2100	0.056*
C8	0.1029 (3)	0.2917 (3)	0.26103 (14)	0.0411 (5)
C9	−0.0705 (3)	0.2553 (3)	0.29035 (13)	0.0377 (5)
C10	−0.0619 (3)	0.0795 (3)	0.32370 (13)	0.0390 (5)
C11	0.1336 (3)	−0.0677 (3)	0.32809 (14)	0.0404 (5)
C12	0.3094 (3)	−0.0359 (3)	0.30170 (15)	0.0492 (6)
H12	0.4389	−0.1349	0.3063	0.059*
C13	0.2947 (3)	0.1401 (3)	0.26888 (16)	0.0505 (6)
H13	0.4148	0.1587	0.2515	0.061*
C14	−0.1131 (5)	1.3253 (4)	0.04590 (17)	0.0626 (8)
H14A	0.0227	1.3280	0.0397	0.094*
H14B	−0.2006	1.4239	0.0778	0.094*
H14C	−0.1706	1.3456	−0.0043	0.094*
C15	−0.2664 (4)	−0.0543 (4)	0.41121 (17)	0.0644 (8)
H15A	−0.2223	−0.1825	0.3972	0.097*
H15B	−0.4086	−0.0101	0.4301	0.097*
H15C	−0.1817	−0.0511	0.4513	0.097*
C16	0.2390 (4)	−0.3320 (4)	0.42227 (17)	0.0568 (7)
C17	0.2612 (5)	−0.5342 (4)	0.43672 (19)	0.0748 (9)
H17A	0.2924	−0.5781	0.4902	0.112*
H17B	0.3714	−0.6114	0.4033	0.112*
H17C	0.1340	−0.5434	0.4260	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0514 (4)	0.0650 (5)	0.1311 (8)	−0.0151 (3)	−0.0205 (4)	0.0421 (5)
O1	0.0657 (13)	0.0466 (11)	0.0789 (15)	0.0036 (9)	0.0188 (11)	−0.0090 (11)
O2	0.0380 (10)	0.0623 (12)	0.1146 (18)	−0.0145 (9)	−0.0277 (11)	0.0122 (11)
O3	0.0386 (9)	0.0504 (10)	0.0747 (13)	−0.0175 (8)	−0.0028 (8)	0.0165 (9)
O4	0.0476 (9)	0.0301 (8)	0.0579 (11)	−0.0087 (7)	−0.0108 (8)	0.0025 (7)
O5	0.121 (2)	0.0643 (14)	0.0713 (15)	−0.0178 (13)	−0.0387 (14)	−0.0035 (11)
N1	0.0378 (10)	0.0385 (11)	0.0580 (13)	−0.0158 (8)	−0.0069 (9)	0.0048 (9)
N2	0.0326 (10)	0.0328 (11)	0.0714 (15)	−0.0065 (8)	0.0028 (11)	0.0088 (11)
C1	0.0351 (12)	0.0438 (14)	0.0662 (17)	−0.0165 (10)	−0.0007 (11)	0.0069 (12)
C2	0.0408 (13)	0.0429 (14)	0.0576 (16)	−0.0130 (10)	−0.0023 (11)	0.0067 (12)
C3	0.0551 (14)	0.0434 (13)	0.0429 (14)	−0.0247 (11)	−0.0005 (11)	0.0003 (11)
C4	0.0502 (14)	0.0562 (15)	0.0571 (16)	−0.0331 (12)	−0.0053 (12)	0.0024 (12)
C5	0.0400 (12)	0.0464 (14)	0.0578 (15)	−0.0200 (11)	−0.0085 (11)	0.0024 (12)
C6	0.0407 (12)	0.0370 (12)	0.0444 (13)	−0.0168 (10)	−0.0012 (10)	−0.0007 (10)
C7	0.0319 (12)	0.0392 (13)	0.0702 (17)	−0.0153 (10)	−0.0014 (11)	−0.0024 (12)
C8	0.0311 (11)	0.0332 (12)	0.0575 (15)	−0.0103 (9)	−0.0066 (10)	−0.0031 (10)
C9	0.0276 (10)	0.0284 (11)	0.0510 (14)	−0.0039 (8)	−0.0048 (10)	−0.0025 (10)
C10	0.0319 (11)	0.0354 (12)	0.0474 (14)	−0.0105 (9)	−0.0040 (10)	−0.0023 (10)
C11	0.0423 (12)	0.0276 (11)	0.0478 (14)	−0.0087 (9)	−0.0110 (10)	−0.0014 (10)
C12	0.0313 (12)	0.0365 (13)	0.0714 (17)	−0.0030 (10)	−0.0127 (11)	−0.0022 (12)
C13	0.0290 (11)	0.0395 (13)	0.0805 (19)	−0.0104 (10)	−0.0060 (11)	−0.0035 (12)
C14	0.0789 (19)	0.0525 (16)	0.0637 (18)	−0.0371 (15)	−0.0055 (15)	0.0103 (14)
C15	0.0564 (16)	0.0651 (18)	0.0666 (19)	−0.0235 (14)	0.0067 (14)	0.0065 (15)
C16	0.0533 (15)	0.0428 (15)	0.0562 (17)	−0.0006 (12)	−0.0052 (13)	0.0015 (13)
C17	0.0739 (19)	0.0481 (16)	0.084 (2)	−0.0107 (14)	−0.0018 (16)	0.0189 (15)

Geometric parameters (Å, º) top

Cl1—C2	1.743 (3)	C7—C8	1.461 (3)
O1—N2	1.221 (3)	C7—H7	0.9300
O2—N2	1.215 (3)	C8—C13	1.395 (3)
O3—C10	1.362 (3)	C8—C9	1.397 (3)
O3—C15	1.417 (3)	C9—C10	1.386 (3)
O4—C16	1.366 (3)	C10—C11	1.394 (3)
O4—C11	1.394 (3)	C11—C12	1.382 (3)
O5—C16	1.186 (3)	C12—C13	1.372 (3)
N1—C7	1.250 (3)	C12—H12	0.9300
N1—C6	1.419 (3)	C13—H13	0.9300
N2—C9	1.478 (3)	C14—H14A	0.9600
C1—C2	1.381 (3)	C14—H14B	0.9600
C1—C6	1.383 (3)	C14—H14C	0.9600
C1—H1	0.9300	C15—H15A	0.9600
C2—C3	1.386 (4)	C15—H15B	0.9600
C3—C4	1.386 (3)	C15—H15C	0.9600
C3—C14	1.508 (3)	C16—C17	1.490 (4)
C4—C5	1.378 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.393 (3)	C17—H17C	0.9600
C5—H5	0.9300

C10—O3—C15	120.89 (19)	O3—C10—C9	116.62 (18)
C16—O4—C11	117.65 (19)	O3—C10—C11	126.4 (2)
C7—N1—C6	121.1 (2)	C9—C10—C11	116.9 (2)
O2—N2—O1	125.6 (2)	C12—C11—C10	120.7 (2)
O2—N2—C9	118.1 (2)	C12—C11—O4	119.86 (19)
O1—N2—C9	116.3 (2)	C10—C11—O4	119.2 (2)
C2—C1—C6	120.3 (2)	C13—C12—C11	120.7 (2)
C2—C1—H1	119.9	C13—C12—H12	119.6
C6—C1—H1	119.9	C11—C12—H12	119.6
C1—C2—C3	122.8 (2)	C12—C13—C8	121.2 (2)
C1—C2—Cl1	118.53 (19)	C12—C13—H13	119.4
C3—C2—Cl1	118.66 (19)	C8—C13—H13	119.4
C4—C3—C2	115.7 (2)	C3—C14—H14A	109.5
C4—C3—C14	120.9 (2)	C3—C14—H14B	109.5
C2—C3—C14	123.4 (2)	H14A—C14—H14B	109.5
C5—C4—C3	122.8 (2)	C3—C14—H14C	109.5
C5—C4—H4	118.6	H14A—C14—H14C	109.5
C3—C4—H4	118.6	H14B—C14—H14C	109.5
C4—C5—C6	120.2 (2)	O3—C15—H15A	109.5
C4—C5—H5	119.9	O3—C15—H15B	109.5
C6—C5—H5	119.9	H15A—C15—H15B	109.5
C1—C6—C5	118.1 (2)	O3—C15—H15C	109.5
C1—C6—N1	116.1 (2)	H15A—C15—H15C	109.5
C5—C6—N1	125.7 (2)	H15B—C15—H15C	109.5
N1—C7—C8	123.6 (2)	O5—C16—O4	122.1 (3)
N1—C7—H7	118.2	O5—C16—C17	127.0 (3)
C8—C7—H7	118.2	O4—C16—C17	110.9 (3)
C13—C8—C9	116.4 (2)	C16—C17—H17A	109.5
C13—C8—C7	118.9 (2)	C16—C17—H17B	109.5
C9—C8—C7	124.71 (19)	H17A—C17—H17B	109.5
C10—C9—C8	124.07 (18)	C16—C17—H17C	109.5
C10—C9—N2	115.70 (19)	H17A—C17—H17C	109.5
C8—C9—N2	120.18 (19)	H17B—C17—H17C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O4	0.96	2.52	2.861 (4)	101
C12—H12···O1ⁱ	0.93	2.58	3.431 (3)	153

Symmetry code: (i) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅ClN₂O₅
M_r	362.76
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.035 (6), 7.672 (6), 17.272 (14)
α, β, γ (°)	83.477 (8), 84.994 (8), 66.697 (7)
V (Å³)	849.7 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.26 × 0.23 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.936, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	5579, 3083, 2207
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.122, 1.05
No. of reflections	3083
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.23

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), 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
C15—H15A···O4	0.96	2.52	2.861 (4)	101.0
C12—H12···O1ⁱ	0.93	2.58	3.431 (3)	152.7

Symmetry code: (i) x+1, y−1, z.

Acknowledgements

This project was sponsored by the Shandong Province Science & Technology Innovation Foundation (People's Republic of China).

References

Bhatia, S. C., Bindlish, J. M., Saini, A. R. & Jain, P. C. (1981). J. Chem. Soc. Dalton Trans. pp. 1773–1779. CSD CrossRef Web of Science Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Costamagna, J., Vargas, J., Latorre, R., Alvarado, A. & Mena, G. (1992). Coord. Chem. Rev. 119, 67–88. CrossRef CAS Web of Science Google Scholar
Qian, S.-S. & Liu, T. (2010). Acta Cryst. E66, o18. 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

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Volume 68| Part 2| February 2012| Page o303

doi:10.1107/S1600536811055590

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-[(E)-(3-Chloro-4-methyl­phen­yl)imino­meth­yl]-2-meth­oxy-3-nitro­phenyl acetate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-[(E)-(3-Chloro-4-methylphenyl)iminomethyl]-2-methoxy-3-nitrophenyl acetate