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accessN-(4-Chlorobenzylidene)-4-methoxyaniline
aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China, and bThe 7th Middle School, Weifang 261061, People's Republic of China
*Correspondence e-mail: ffjian2008@163.com
The title compound, C14H12ClNO, was prepared by the reaction of 4-methoxyaniline and 4-chlorobenzaldehyde in ethanol at 367 K. The molecule is almost planar, with a dihedral angle between the two benzene rings of 9.1 (2)° and an r.m.s. deviation from the mean plane through all non-H atoms in the molecule of 0.167 Å.
Related literature
For applications of Schiff base compounds, see: Deschamps et al. (2003![[Deschamps, P., Kulkarni, P. P. & Sarkar, B. (2003). Inorg. Chem., 42, 7366-7368.]](../../../../../../logos/arrows/e_arr.gif "Deschamps, P., Kulkarni, P. P. & Sarkar, B. (2003). Inorg. Chem., 42, 7366-7368.")
); Rozwadowski et al. (1999); Tarafder et al. (2000). For a related structure, see: Jian et al. (2006).
![[Scheme 1]](sj2527scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); 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
contains datablocks global, I. DOI: 10.1107/S1600536808026111/sj2527sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808026111/sj2527Isup2.hkl
A mixture of 4-methoxyaniline 2.46 g (0.02 mol) and 4-chlorobenzaldehyde 2.8 g (0.02 mol) was stirred in ethanol (50 mL) at 367 K for 2 h, to give the title compound (3.9 g, yield 81%). Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone and ethanol(1:1) at room temperature.
All H-atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.93Å, Uiso=1.2Ueq(C) for aromatic and 0.96Å, Uiso = 1.5Ueq(C) for CH3 atoms.
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).
![[Figure 1]](./sj2527fig1thm.gif) | Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
| C14H12ClNO | F(000) = 512 |
| Mr = 245.70 | Dx = 1.326 Mg m−3 |
| Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2c -2n | Cell parameters from 2092 reflections |
| a = 6.1055 (9) Å | θ = 2.9–28.3° |
| b = 7.3392 (11) Å | µ = 0.29 mm−1 |
| c = 27.469 (4) Å | T = 293 K |
| V = 1230.9 (3) Å3 | Block, yellow |
| Z = 4 | 0.20 × 0.15 × 0.11 mm |
| Bruker SMART CCD area-detector diffractometer | 2092 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.022 |
| Graphite monochromator | θmax = 28.3°, θmin = 2.9° |
| ϕ and ω scans | h = −8→4 |
| 7232 measured reflections | k = −9→9 |
| 2806 independent reflections | l = −36→33 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.04P)2 + 0.0836P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 2806 reflections | Δρmax = 0.14 e Å−3 |
| 154 parameters | Δρmin = −0.16 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 1450 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (7) |
| C14H12ClNO | V = 1230.9 (3) Å3 |
| Mr = 245.70 | Z = 4 |
| Orthorhombic, Pna21 | Mo Kα radiation |
| a = 6.1055 (9) Å | µ = 0.29 mm−1 |
| b = 7.3392 (11) Å | T = 293 K |
| c = 27.469 (4) Å | 0.20 × 0.15 × 0.11 mm |
| Bruker SMART CCD area-detector diffractometer | 2092 reflections with I > 2σ(I) |
| 7232 measured reflections | Rint = 0.022 |
| 2806 independent reflections |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.088 | Δρmax = 0.14 e Å−3 |
| S = 1.01 | Δρmin = −0.16 e Å−3 |
| 2806 reflections | Absolute structure: Flack (1983), 1450 Friedel pairs |
| 154 parameters | Absolute structure parameter: −0.01 (7) |
| 1 restraint |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.77772 (12) | 0.00540 (10) | 0.23599 (3) | 0.0862 (2) | |
| O1 | −0.0611 (2) | −0.01368 (19) | 0.64134 (5) | 0.0560 (4) | |
| N1 | 0.2457 (3) | 0.0122 (2) | 0.45058 (6) | 0.0463 (4) | |
| C1 | −0.2589 (4) | 0.0731 (4) | 0.65469 (10) | 0.0750 (7) | |
| H1B | −0.2859 | 0.0539 | 0.6887 | 0.112* | |
| H1C | −0.3775 | 0.0230 | 0.6361 | 0.112* | |
| H1D | −0.2475 | 0.2014 | 0.6483 | 0.112* | |
| C2 | 0.0048 (3) | −0.0027 (2) | 0.59389 (7) | 0.0421 (4) | |
| C3 | 0.1994 (3) | −0.0915 (2) | 0.58341 (7) | 0.0446 (4) | |
| H3A | 0.2739 | −0.1522 | 0.6081 | 0.053* | |
| C4 | 0.2838 (3) | −0.0909 (3) | 0.53699 (7) | 0.0456 (4) | |
| H4A | 0.4144 | −0.1513 | 0.5305 | 0.055* | |
| C5 | 0.1737 (3) | 0.0005 (2) | 0.49944 (7) | 0.0395 (4) | |
| C6 | −0.0225 (3) | 0.0856 (3) | 0.51062 (6) | 0.0436 (4) | |
| H6A | −0.0996 | 0.1442 | 0.4860 | 0.052* | |
| C7 | −0.1074 (3) | 0.0862 (2) | 0.55747 (7) | 0.0451 (4) | |
| H7A | −0.2384 | 0.1458 | 0.5642 | 0.054* | |
| C8 | 0.4424 (3) | −0.0157 (2) | 0.43961 (7) | 0.0475 (5) | |
| H8A | 0.5407 | −0.0439 | 0.4644 | 0.057* | |
| C9 | 0.5235 (3) | −0.0060 (2) | 0.38958 (8) | 0.0456 (4) | |
| C10 | 0.3951 (4) | 0.0631 (3) | 0.35228 (7) | 0.0537 (5) | |
| H10A | 0.2559 | 0.1075 | 0.3592 | 0.064* | |
| C11 | 0.4712 (4) | 0.0666 (3) | 0.30525 (8) | 0.0595 (6) | |
| H11A | 0.3842 | 0.1133 | 0.2804 | 0.071* | |
| C12 | 0.6790 (4) | 0.0000 (3) | 0.29508 (8) | 0.0572 (6) | |
| C13 | 0.8091 (3) | −0.0666 (3) | 0.33165 (8) | 0.0579 (5) | |
| H13A | 0.9480 | −0.1115 | 0.3247 | 0.069* | |
| C14 | 0.7321 (3) | −0.0665 (3) | 0.37880 (7) | 0.0534 (5) | |
| H14A | 0.8221 | −0.1079 | 0.4038 | 0.064* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0943 (5) | 0.1126 (5) | 0.0517 (3) | −0.0069 (4) | 0.0194 (4) | −0.0127 (3) |
| O1 | 0.0570 (9) | 0.0702 (10) | 0.0409 (7) | 0.0069 (7) | 0.0025 (7) | −0.0003 (6) |
| N1 | 0.0453 (10) | 0.0487 (10) | 0.0448 (10) | 0.0027 (7) | −0.0005 (7) | −0.0006 (7) |
| C1 | 0.0614 (15) | 0.104 (2) | 0.0598 (14) | 0.0089 (13) | 0.0097 (11) | −0.0055 (13) |
| C2 | 0.0414 (9) | 0.0408 (9) | 0.0440 (10) | −0.0062 (7) | −0.0034 (9) | −0.0031 (8) |
| C3 | 0.0429 (9) | 0.0450 (10) | 0.0459 (11) | 0.0016 (8) | −0.0062 (8) | 0.0036 (8) |
| C4 | 0.0396 (10) | 0.0457 (10) | 0.0516 (11) | 0.0073 (8) | −0.0017 (8) | 0.0024 (8) |
| C5 | 0.0408 (10) | 0.0361 (9) | 0.0417 (9) | −0.0022 (7) | −0.0009 (7) | −0.0013 (7) |
| C6 | 0.0409 (10) | 0.0411 (10) | 0.0487 (11) | 0.0043 (8) | −0.0080 (8) | 0.0020 (8) |
| C7 | 0.0397 (10) | 0.0444 (9) | 0.0511 (11) | 0.0048 (8) | −0.0023 (8) | −0.0014 (8) |
| C8 | 0.0453 (11) | 0.0527 (11) | 0.0446 (10) | −0.0005 (9) | −0.0036 (9) | −0.0018 (9) |
| C9 | 0.0435 (10) | 0.0449 (10) | 0.0484 (10) | −0.0041 (8) | −0.0011 (9) | −0.0025 (8) |
| C10 | 0.0479 (11) | 0.0593 (12) | 0.0540 (12) | 0.0032 (10) | 0.0019 (9) | −0.0013 (9) |
| C11 | 0.0598 (14) | 0.0688 (14) | 0.0498 (12) | 0.0060 (11) | −0.0051 (10) | 0.0013 (9) |
| C12 | 0.0660 (14) | 0.0581 (13) | 0.0476 (12) | −0.0085 (11) | 0.0123 (10) | −0.0092 (10) |
| C13 | 0.0473 (12) | 0.0646 (13) | 0.0617 (14) | 0.0032 (10) | 0.0059 (10) | −0.0055 (11) |
| C14 | 0.0473 (12) | 0.0620 (13) | 0.0508 (12) | 0.0043 (9) | −0.0002 (9) | 0.0018 (9) |
| Cl1—C12 | 1.732 (2) | C6—C7 | 1.387 (2) |
| O1—C2 | 1.366 (2) | C6—H6A | 0.9300 |
| O1—C1 | 1.414 (3) | C7—H7A | 0.9300 |
| N1—C8 | 1.255 (2) | C8—C9 | 1.463 (3) |
| N1—C5 | 1.415 (3) | C8—H8A | 0.9300 |
| C1—H1B | 0.9600 | C9—C14 | 1.381 (3) |
| C1—H1C | 0.9600 | C9—C10 | 1.386 (3) |
| C1—H1D | 0.9600 | C10—C11 | 1.373 (3) |
| C2—C7 | 1.377 (3) | C10—H10A | 0.9300 |
| C2—C3 | 1.386 (2) | C11—C12 | 1.388 (3) |
| C3—C4 | 1.375 (2) | C11—H11A | 0.9300 |
| C3—H3A | 0.9300 | C12—C13 | 1.371 (3) |
| C4—C5 | 1.402 (3) | C13—C14 | 1.378 (3) |
| C4—H4A | 0.9300 | C13—H13A | 0.9300 |
| C5—C6 | 1.386 (3) | C14—H14A | 0.9300 |
| C2—O1—C1 | 118.19 (17) | C2—C7—H7A | 120.4 |
| C8—N1—C5 | 121.00 (17) | C6—C7—H7A | 120.4 |
| O1—C1—H1B | 109.5 | N1—C8—C9 | 122.78 (18) |
| O1—C1—H1C | 109.5 | N1—C8—H8A | 118.6 |
| H1B—C1—H1C | 109.5 | C9—C8—H8A | 118.6 |
| O1—C1—H1D | 109.5 | C14—C9—C10 | 118.7 (2) |
| H1B—C1—H1D | 109.5 | C14—C9—C8 | 119.87 (19) |
| H1C—C1—H1D | 109.5 | C10—C9—C8 | 121.40 (17) |
| O1—C2—C7 | 125.07 (16) | C11—C10—C9 | 120.7 (2) |
| O1—C2—C3 | 115.02 (17) | C11—C10—H10A | 119.6 |
| C7—C2—C3 | 119.91 (18) | C9—C10—H10A | 119.6 |
| C4—C3—C2 | 120.82 (17) | C10—C11—C12 | 119.5 (2) |
| C4—C3—H3A | 119.6 | C10—C11—H11A | 120.3 |
| C2—C3—H3A | 119.6 | C12—C11—H11A | 120.3 |
| C3—C4—C5 | 120.27 (17) | C13—C12—C11 | 120.5 (2) |
| C3—C4—H4A | 119.9 | C13—C12—Cl1 | 119.55 (17) |
| C5—C4—H4A | 119.9 | C11—C12—Cl1 | 119.92 (19) |
| C6—C5—C4 | 117.86 (18) | C12—C13—C14 | 119.42 (18) |
| C6—C5—N1 | 116.83 (16) | C12—C13—H13A | 120.3 |
| C4—C5—N1 | 125.31 (16) | C14—C13—H13A | 120.3 |
| C5—C6—C7 | 122.00 (17) | C13—C14—C9 | 121.1 (2) |
| C5—C6—H6A | 119.0 | C13—C14—H14A | 119.5 |
| C7—C6—H6A | 119.0 | C9—C14—H14A | 119.5 |
| C2—C7—C6 | 119.11 (17) |
Experimental details
| Crystal data | |
| Chemical formula | C14H12ClNO |
| Mr | 245.70 |
| Crystal system, space group | Orthorhombic, Pna21 |
| Temperature (K) | 293 |
| a, b, c (Å) | 6.1055 (9), 7.3392 (11), 27.469 (4) |
| V (Å3) | 1230.9 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.29 |
| Crystal size (mm) | 0.20 × 0.15 × 0.11 |
| Data collection | |
| Diffractometer | Bruker SMART CCD area-detector diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7232, 2806, 2092 |
| Rint | 0.022 |
| (sin θ/λ)max (Å−1) | 0.666 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.088, 1.01 |
| No. of reflections | 2806 |
| No. of parameters | 154 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.14, −0.16 |
| Absolute structure | Flack (1983), 1450 Friedel pairs |
| Absolute structure parameter | −0.01 (7) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
References
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deschamps, P., Kulkarni, P. P. & Sarkar, B. (2003). Inorg. Chem., 42, 7366–7368. Web of Science CSD CrossRef PubMed CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jian, F.-F., Zhuang, R.-R., Wang, K.-F., Zhao, P.-S. & Xiao, H.-L. (2006). Acta Cryst. E62, o3198–o3199. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rozwadowski, Z., Majewski, E., Dziembowska, T. & Hansen, P. E. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 2809–2817. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tarafder, M. T. H., Ali, M. A., Wee, D. J., Azahari, K., Silong, S. & Crouse, K. A. (2000). Transition Met. Chem. 25, 456–460. Web of Science CrossRef CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Schiff bases have been used extensively as ligands in the field of coordination chemistry (Jian et al., 2006), and have antimicrobial (Tarafder et al., 2000) and anticancer applications (Deschamps et al., 2003). Additional recent interest in Schiff base compounds comes from their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al.,1999). We report here the synthesis and structure of the title Schiff base compound, I, Fig. 1.
The molecule is almost planar with a dihedral angle between the C2···C7 and C9···C13 benzene rings of 9.1 (2)° and an rms deviation from the meanplane through all non-hydrogen atoms in the molecule of 0.167. The C═N bond distance (1.255 (2) Å) is in reasonable agreement with that observed in a similar compound (Jian et al., 2006).