organic compounds
(E)-2-{[(5-Chloro-2-methoxyphenyl)imino]methyl}-4-nitrophenol
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
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 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 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.
are biologically active, making this class of compounds important for many different disciplines in chemistry. Moreover, some show phototochromism which can be used for radiation intensity measurements, display systems or optical devices (YıldızThe 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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 1530590
https://doi.org/10.1107/S2414314617001778/wm4037sup1.cif
contains datablocks I, shelx. DOI: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
Data collection: X-AREA (Stoe & Cie, 2002); cell
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).C14H11ClN2O4 | F(000) = 632 |
Mr = 306.70 | Dx = 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 |
Stoe IPDS 2 diffractometer | 1527 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 1.6° |
rotation method scans | h = −17→17 |
10508 measured reflections | k = −5→6 |
2679 independent reflections | l = −27→27 |
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(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
2679 reflections | Δρmax = 0.13 e Å−3 |
194 parameters | Δρmin = −0.18 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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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