(E)-2-{[(5-Chloro-2-meth­oxy­phen­yl)imino]­meth­yl}-4-nitro­phenol

Öv Bodur, G.S.; Yavuz, M.; Dege, N.; Bülbül, H.; Ağar, E.

doi:10.1107/S2414314617001778

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170177

https://doi.org/10.1107/S2414314617001778

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(E)-2-{[(5-Chloro-2-methoxyphenyl)imino]methyl}-4-nitrophenol

Gönül Sevde Öv Bodur,^a ^* Metin Yavuz,^a Necmi Dege,^b Hakan Bülbül ^a and Erbil Ağar ^b

^aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, TR-55139 Samsun, Turkey, and ^bDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayıs University, Kurupelit, 55139 Samsun, Turkey
^*Correspondence e-mail: gonulsevdee@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 January 2017; accepted 1 February 2017; online 14 February 2017)

The title compound, C₁₄H₁₁ClN₂O₄, is a Schiff base. Its molecule is approximatelly planar, with a maximum deviation of 0.096 (4) Å from planarity for the methyl C atom of the methoxy group. The dihedral angle between the 5-chloro-2-methoxyphenyl ring and the phenol ring is 2.40 (10)°. In the crystal structure, intermolecular C—H⋯O hydrogen bonds and π–π stacking interactions consolidate the crystal packing.

Keywords: crystal structure; Schiff base; nitrophenol; hydrogen bonding; π–π stacking interactions.

CCDC reference: 1530590

Structure description

Many Schiff bases are biologically active, making this class of compounds important for many different disciplines in chemistry. Moreover, some Schiff bases show phototochromism which can be used for radiation intensity measurements, display systems or optical devices (Yıldız et al., 2005 ; Hadjoudis et al., 1987 ). Apart from these areas, Schiff base are versatile complexing agents, with the products known to show antifungal, antibacterial, herbicidal, anticancer, antiviral, anticonvulsant, diuretic or cytotoxic properties (Cozzi & Alesi, 2004 ; Shebl & Khalil, 2015 ; Tarafder et al., 2002 ). As another class of compounds, nitroaromatics are common components of explosives, dyes and pesticides and have manifold use in organic synthesis as starting materials or intermediates (Yan et al., 2006 ; Soojhawon et al., 2005 ). Aromatic compounds containing multiple nitro substituents are known to resist electrophilic attack by oxgenases (Hallas & Alexander, 1983 ). On the other hand, nitroaromatics are industrial waste, directly polluting the environment due to their moderate solubility in water, hence poisoning rivers, ponds and soil (Yan et al., 2006; Soojhawon et al., 2005). We have synthesized a Schiff base with an aromatic nitro substituent and report herein on its crystal structure.

The title molecule (Fig. 1) is essentially planar, with a maximum deviation of 0.096 (4) Å from planarity for the methyl C atom (C14) of the methoxy group. The C7—N2 bond length of 1.270 (3) Å and the C5—O3 bond lengths of 1.328 (3) Å are consistent with a double bond and a single bond, respectively, and are comparable with those of related structures (Kılıç et al., 2009 ). The entities A (phenol ring; C1–C6/O3), B (nitro group; O1/O2/N1) and C (5-chloro-2-methoxyphenyl ring; C8–C13/O4/ C14/CI1) are inclined by dihedral angles of A/B = 3.1 (3)°, A/C = 2.40 (10)° and (A+B)/C = 2.15 (9)°. An intramolecular O—H⋯N hydrogen bond stabilizes the molecular conformation whereas intermolecular (methyl)C—H⋯O(methoxy) and (imine)C—H⋯O(nitro) hydrogen bonds lead to the formation of sheets extending parallel to (210) (Fig. 2, Table 1). A plane-to-plane distance of 3.379 (3) Å for parallel-aligned sheets indicates the presence of π–π stacking interactions in the crystal.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H15⋯N2	0.84 (3)	1.84 (3)	2.606 (3)	151 (3)
C7—H7⋯O1ⁱ	0.93	2.42	3.325 (3)	163
C14—H14A⋯O4ⁱⁱ	0.96	2.58	3.516 (4)	166
Symmetry codes: (i) -x+1, -y+3, -z+1; (ii) -x, -y+1, -z+1.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Figure 2
A partial packing view along [100]. Dashed lines indicate hydrogen bonds.

Synthesis and crystallization

The title compound was prepared by refluxing a mixture of 2-hydroxy-5-nitrobenzaldehyde (0.0069 g, 0.413 mmol) in 20 ml ethanol and 3-chloro-4-methoxyaniline (0.0065 g, 0.413 mmol) in 20 ml ethanol for one hour. Crystals suitable for X-ray analysis were obtained by slow evaporation of the resulting solution (yield 35%; m.p 450–452 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClN₂O₄
M_r	306.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.3727 (9), 4.8669 (4), 22.3233 (13)
β (°)	118.859 (9)
V (Å³)	1367.60 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.71 × 0.30 × 0.05

Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10508, 2679, 1527
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.106, 0.94
No. of reflections	2679
No. of parameters	194
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.18
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ).

Structural data

CCDC reference: 1530590

Crystal structure: contains datablocks I, shelx. DOI: https://doi.org/10.1107/S2414314617001778/wm4037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001778/wm4037Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617001778/wm4037Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

(E)-2-{[(5-Chloro-2-methoxyphenyl)imino]methyl}-4-nitrophenol top

Crystal data top

C₁₄H₁₁ClN₂O₄	F(000) = 632
M_r = 306.70	D_x = 1.490 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.3727 (9) Å	Cell parameters from 453 reflections
b = 4.8669 (4) Å	θ = 2.8–26.5°
c = 22.3233 (13) Å	µ = 0.30 mm⁻¹
β = 118.859 (9)°	T = 293 K
V = 1367.60 (19) Å³	Stick, orange
Z = 4	0.71 × 0.30 × 0.05 mm

Data collection top

Stoe IPDS 2 diffractometer	1527 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 1.6°
rotation method scans	h = −17→17
10508 measured reflections	k = −5→6
2679 independent reflections	l = −27→27

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0521P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max < 0.001
2679 reflections	Δρ_max = 0.13 e Å⁻³
194 parameters	Δρ_min = −0.18 e Å⁻³

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
N1	0.52416 (15)	1.7724 (4)	0.62967 (10)	0.0621 (5)
N2	0.21754 (15)	0.8722 (4)	0.46453 (9)	0.0548 (5)
O1	0.55958 (16)	1.7922 (4)	0.58993 (10)	0.0904 (6)
O2	0.55351 (15)	1.9177 (4)	0.68000 (9)	0.0819 (6)
O3	0.20231 (15)	1.0208 (4)	0.57164 (11)	0.0773 (6)
O4	0.06221 (14)	0.5188 (4)	0.43672 (9)	0.0827 (6)
Cl5	0.24175 (6)	0.56490 (18)	0.25064 (4)	0.0910 (3)
C1	0.40681 (17)	1.4090 (5)	0.55759 (11)	0.0532 (6)
H1	0.437436	1.426791	0.529395	0.064*
C2	0.44190 (17)	1.5699 (5)	0.61496 (10)	0.0516 (5)
C3	0.39872 (19)	1.5455 (5)	0.65855 (11)	0.0627 (6)
H3	0.423828	1.653642	0.697654	0.075*
C4	0.3190 (2)	1.3609 (5)	0.64320 (12)	0.0678 (7)
H4	0.289785	1.344033	0.672215	0.081*
C5	0.28050 (19)	1.1971 (5)	0.58499 (12)	0.0572 (6)
C6	0.32592 (17)	1.2200 (5)	0.54146 (10)	0.0504 (5)
C7	0.29030 (18)	1.0508 (5)	0.48111 (11)	0.0567 (6)
H7	0.321734	1.073469	0.453501	0.068*
C8	0.18388 (18)	0.7040 (5)	0.40607 (11)	0.0532 (5)
C9	0.22709 (19)	0.7136 (5)	0.36221 (11)	0.0593 (6)
H9	0.281618	0.836500	0.370621	0.071*
C10	0.18942 (19)	0.5422 (5)	0.30648 (12)	0.0612 (6)
C11	0.1098 (2)	0.3565 (5)	0.29338 (12)	0.0676 (7)
H11	0.085619	0.239788	0.255838	0.081*
C12	0.0665 (2)	0.3450 (5)	0.33613 (12)	0.0675 (7)
H12	0.012689	0.219286	0.327311	0.081*
C13	0.10144 (18)	0.5171 (5)	0.39218 (12)	0.0588 (6)
C14	−0.0258 (3)	0.3385 (8)	0.42157 (18)	0.1160 (13)
H14A	−0.046574	0.357148	0.456270	0.139*
H14B	−0.084445	0.386065	0.377899	0.139*
H14C	−0.004954	0.151962	0.420421	0.139*
H15	0.190 (3)	0.938 (7)	0.5353 (18)	0.110 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0579 (12)	0.0628 (14)	0.0635 (12)	−0.0097 (10)	0.0277 (10)	−0.0060 (11)
N2	0.0572 (11)	0.0488 (12)	0.0588 (11)	−0.0081 (10)	0.0282 (9)	−0.0033 (9)
O1	0.0925 (14)	0.1061 (17)	0.0973 (14)	−0.0438 (12)	0.0655 (12)	−0.0278 (12)
O2	0.0839 (13)	0.0805 (13)	0.0724 (11)	−0.0243 (10)	0.0307 (10)	−0.0242 (11)
O3	0.0841 (13)	0.0825 (15)	0.0841 (13)	−0.0298 (11)	0.0555 (11)	−0.0121 (11)
O4	0.0831 (12)	0.0952 (15)	0.0797 (11)	−0.0399 (11)	0.0470 (10)	−0.0193 (10)
Cl5	0.1001 (6)	0.1078 (6)	0.0782 (4)	0.0006 (5)	0.0534 (4)	−0.0180 (4)
C1	0.0551 (13)	0.0577 (15)	0.0540 (12)	−0.0050 (12)	0.0319 (10)	0.0000 (11)
C2	0.0520 (13)	0.0527 (14)	0.0506 (12)	−0.0054 (11)	0.0252 (10)	0.0012 (11)
C3	0.0777 (17)	0.0616 (17)	0.0530 (13)	−0.0057 (14)	0.0349 (12)	−0.0048 (12)
C4	0.0865 (18)	0.0710 (19)	0.0637 (15)	−0.0118 (15)	0.0504 (14)	−0.0023 (13)
C5	0.0620 (14)	0.0535 (15)	0.0636 (14)	−0.0066 (12)	0.0364 (12)	0.0032 (12)
C6	0.0518 (13)	0.0535 (15)	0.0498 (11)	−0.0027 (11)	0.0276 (10)	0.0022 (11)
C7	0.0593 (14)	0.0601 (15)	0.0565 (13)	−0.0062 (13)	0.0324 (11)	−0.0009 (12)
C8	0.0564 (13)	0.0446 (13)	0.0543 (12)	0.0012 (11)	0.0234 (11)	0.0014 (11)
C9	0.0606 (14)	0.0536 (15)	0.0625 (14)	−0.0020 (12)	0.0288 (12)	−0.0045 (12)
C10	0.0642 (15)	0.0584 (16)	0.0579 (14)	0.0083 (13)	0.0271 (12)	−0.0004 (12)
C11	0.0743 (17)	0.0558 (17)	0.0550 (14)	0.0054 (13)	0.0171 (13)	−0.0070 (12)
C12	0.0689 (16)	0.0529 (16)	0.0669 (16)	−0.0100 (13)	0.0218 (13)	−0.0019 (13)
C13	0.0575 (14)	0.0529 (16)	0.0587 (13)	−0.0042 (12)	0.0224 (12)	0.0032 (11)
C14	0.104 (3)	0.149 (3)	0.113 (2)	−0.071 (2)	0.067 (2)	−0.038 (2)

Geometric parameters (Å, º) top

N1—O2	1.218 (2)	C4—H4	0.9300
N1—O1	1.221 (2)	C5—C6	1.413 (3)
N1—C2	1.450 (3)	C6—C7	1.445 (3)
N2—C7	1.270 (3)	C7—H7	0.9300
N2—C8	1.413 (3)	C8—C9	1.391 (3)
O3—C5	1.328 (3)	C8—C13	1.405 (3)
O3—H15	0.84 (3)	C9—C10	1.374 (3)
O4—C13	1.359 (3)	C9—H9	0.9300
O4—C14	1.439 (3)	C10—C11	1.374 (4)
Cl5—C10	1.743 (2)	C11—C12	1.369 (4)
C1—C2	1.373 (3)	C11—H11	0.9300
C1—C6	1.387 (3)	C12—C13	1.383 (3)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.389 (3)	C14—H14A	0.9600
C3—C4	1.363 (3)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C4—C5	1.391 (3)

O2—N1—O1	123.0 (2)	C6—C7—H7	118.9
O2—N1—C2	119.0 (2)	C9—C8—C13	118.8 (2)
O1—N1—C2	118.00 (19)	C9—C8—N2	124.1 (2)
C7—N2—C8	122.17 (18)	C13—C8—N2	117.09 (19)
C5—O3—H15	107 (2)	C10—C9—C8	120.2 (2)
C13—O4—C14	116.9 (2)	C10—C9—H9	119.9
C2—C1—C6	120.34 (19)	C8—C9—H9	119.9
C2—C1—H1	119.8	C11—C10—C9	121.1 (2)
C6—C1—H1	119.8	C11—C10—Cl5	119.48 (19)
C1—C2—C3	121.2 (2)	C9—C10—Cl5	119.5 (2)
C1—C2—N1	119.43 (18)	C12—C11—C10	119.4 (2)
C3—C2—N1	119.4 (2)	C12—C11—H11	120.3
C4—C3—C2	119.1 (2)	C10—C11—H11	120.3
C4—C3—H3	120.5	C11—C12—C13	121.1 (2)
C2—C3—H3	120.5	C11—C12—H12	119.4
C3—C4—C5	121.3 (2)	C13—C12—H12	119.4
C3—C4—H4	119.3	O4—C13—C12	124.6 (2)
C5—C4—H4	119.3	O4—C13—C8	116.0 (2)
O3—C5—C4	119.5 (2)	C12—C13—C8	119.4 (2)
O3—C5—C6	121.2 (2)	O4—C14—H14A	109.5
C4—C5—C6	119.3 (2)	O4—C14—H14B	109.5
C1—C6—C5	118.8 (2)	H14A—C14—H14B	109.5
C1—C6—C7	119.69 (18)	O4—C14—H14C	109.5
C5—C6—C7	121.5 (2)	H14A—C14—H14C	109.5
N2—C7—C6	122.21 (19)	H14B—C14—H14C	109.5
N2—C7—H7	118.9

C6—C1—C2—C3	0.9 (3)	C5—C6—C7—N2	−0.7 (3)
C6—C1—C2—N1	−178.0 (2)	C7—N2—C8—C9	1.0 (3)
O2—N1—C2—C1	178.7 (2)	C7—N2—C8—C13	−178.9 (2)
O1—N1—C2—C1	0.0 (3)	C13—C8—C9—C10	−0.1 (3)
O2—N1—C2—C3	−0.2 (3)	N2—C8—C9—C10	180.0 (2)
O1—N1—C2—C3	−178.9 (2)	C8—C9—C10—C11	−0.8 (4)
C1—C2—C3—C4	−1.0 (4)	C8—C9—C10—Cl5	178.00 (18)
N1—C2—C3—C4	177.9 (2)	C9—C10—C11—C12	0.9 (4)
C2—C3—C4—C5	0.1 (4)	Cl5—C10—C11—C12	−177.96 (19)
C3—C4—C5—O3	−179.6 (2)	C10—C11—C12—C13	0.0 (4)
C3—C4—C5—C6	0.9 (4)	C14—O4—C13—C12	−3.6 (4)
C2—C1—C6—C5	0.1 (3)	C14—O4—C13—C8	177.0 (3)
C2—C1—C6—C7	−179.6 (2)	C11—C12—C13—O4	179.7 (2)
O3—C5—C6—C1	179.5 (2)	C11—C12—C13—C8	−1.0 (4)
C4—C5—C6—C1	−1.0 (3)	C9—C8—C13—O4	−179.6 (2)
O3—C5—C6—C7	−0.8 (4)	N2—C8—C13—O4	0.2 (3)
C4—C5—C6—C7	178.7 (2)	C9—C8—C13—C12	1.0 (3)
C8—N2—C7—C6	−179.0 (2)	N2—C8—C13—C12	−179.1 (2)
C1—C6—C7—N2	179.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H15···N2	0.84 (3)	1.84 (3)	2.606 (3)	151 (3)
C7—H7···O1ⁱ	0.93	2.42	3.325 (3)	163
C14—H14A···O4ⁱⁱ	0.96	2.58	3.516 (4)	166

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

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