PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o253.
Published online 2009 January 8. doi:  10.1107/S1600536809000300
PMCID: PMC2968176

4-Chloro-N-(3,4,5-trimethoxy­benzyl­idene)aniline

Abstract

The title compound, C16H16ClNO3, is a Schiff base displaying a trans configuration of the C=N double bond. In the crystal structure, inter­molecular C—H(...)N and bifurcated C—H(...)(O,O) hydrogen bonds are observed.

Related literature

For backgroud and related structures, see: Khalaji et al. (2008 [triangle]); Khalaji & Harrison (2008 [triangle]); Khalaji et al. (2007 [triangle]); Zhang (2008 [triangle]); Akkurt et al. (2008 [triangle]); Kashmiri et al. (2008 [triangle]); Ren & Jian (2008 [triangle]). For the synthesis of the title compound, see: Khalaji & Ng (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o253-scheme1.jpg

Experimental

Crystal data

  • C16H16ClNO3
  • M r = 305.75
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o253-efi1.jpg
  • a = 7.2012 (2) Å
  • b = 8.18700 (10) Å
  • c = 12.9734 (3) Å
  • β = 105.050 (2)°
  • V = 738.63 (3) Å3
  • Z = 2
  • Cu Kα radiation
  • μ = 2.37 mm−1
  • T = 120 K
  • 0.22 × 0.20 × 0.11 mm

Data collection

  • Oxford Diffraction Gemini diffractometer
  • Absorption correction: numerical [Clark & Reid (1995 [triangle]) in CrysAlis RED (Oxford Diffraction, 2008 [triangle])] T min = 0.680, T max = 0.809
  • 5670 measured reflections
  • 2225 independent reflections
  • 2039 reflections with I > 3σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.109
  • S = 1.93
  • 2225 reflections
  • 189 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.21 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 915 Friedel pairs
  • Flack parameter: 0.06 (2)

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003 [triangle]); program(s) used to refine structure: JANA2006 (Petříček et al., 2007 [triangle]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 [triangle]); software used to prepare material for publication: JANA2006.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000300/bt2844sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000300/bt2844Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Gorgan University of Agricultural Sciences and Natural Resources (GUASNR) and the Institute of Physics of the ASCR (grant No 202/07/J007) for supporting this study. ADK thanks Dr Jan Fabry (Institute of Physics of ASCR) for his collaboration.

supplementary crystallographic information

Comment

Studies on the Schiff-base compounds, products of condensation between aldehydes (or ketones) and amines, have received a lot of attention in recent years, (Khalaji et al., 2008; Khalaji & Harrison, 2008; Khalaji et al.,2007; Zhang, 2008; Akkurt et al., 2008; Kashmiri et al., 2008; Ren & Jian, 2008). As a continuation of these studies we present the crystal structure of C16H16ClNO3.

The molecular structure of the title compound is shown in Fig. 1. Bond lengths and angles are comparable with those observed in similar compounds (Khalaji et al., 2008; Khalaji & Harrison, 2008; Khalaji et al.,2007; Zhang, 2008; Akkurt et al., 2008; Kashmiri et al., 2008; Ren & Jian, 2008). In the crystal structure, intermolecular C—H···N and C—H···O hydrogen bonds are observed.

Experimental

The title compound was synthesized using a method analogous to the literature procedure of Khalaji and Ng (2008). Crystals appropriate for data collection were obtained by slow evaporation from methanol-chloroform (1:5 v/v) at a room temperature (yield 83%).

Refinement

All the H atoms were found in difference Fourier maps, but they were constrained to ideal positions. The isotropic atomic displacement parameters of hydrogen atoms were set to 1.2Ueq of the parent atom.

Figures

Fig. 1.
The molecular structure of the title compound with atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
The packing of (I) viewed along a, with hydrogen bonds shown as dashed lines.

Crystal data

C16H16ClNO3F(000) = 320
Mr = 305.75Dx = 1.379 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ybCell parameters from 4239 reflections
a = 7.2012 (2) Åθ = 3.5–62.6°
b = 8.1870 (1) ŵ = 2.37 mm1
c = 12.9734 (3) ÅT = 120 K
β = 105.050 (2)°Prism, colorless
V = 738.63 (3) Å30.22 × 0.20 × 0.11 mm
Z = 2

Data collection

Oxford Diffraction Gemini diffractometer with Xcalibur goniometer, Atlas detector and Gemini ultra Cu source2225 independent reflections
Radiation source: X-ray tube2039 reflections with I > 3σ(I)
mirrorRint = 0.048
Detector resolution: 20.7567 pixels mm-1θmax = 62.7°, θmin = 3.5°
rotation method data acquisition using ω scansh = −8→7
Absorption correction: numerical [based on the crystal shape, using the method implemented in CrysAlis RED (Oxford Diffraction, 2008) according to Clark & Reid (1995)]k = −9→9
Tmin = 0.680, Tmax = 0.809l = −14→14
5670 measured reflections

Refinement

Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0016I2]
wR(F2) = 0.109(Δ/σ)max = 0.013
S = 1.93Δρmax = 0.28 e Å3
2225 reflectionsΔρmin = −0.21 e Å3
189 parametersAbsolute structure: Flack (1983), 915 Friedel pairs
0 restraintsFlack parameter: 0.06 (2)
65 constraints

Special details

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.00790 (13)0.16442 (1)0.00937 (6)0.0366 (3)
O11.2823 (3)0.6425 (3)0.64185 (15)0.0252 (7)
O21.4726 (3)0.8288 (3)0.53638 (16)0.0255 (7)
O31.3717 (3)0.8527 (3)0.32476 (16)0.0298 (8)
N10.7360 (4)0.5116 (4)0.2085 (2)0.0261 (10)
C11.2081 (4)0.6506 (4)0.5342 (2)0.0199 (9)
C21.3141 (5)0.7435 (4)0.4792 (2)0.0220 (10)
C31.2528 (5)0.7593 (4)0.3685 (3)0.0226 (11)
C41.0855 (4)0.6828 (4)0.3111 (2)0.0239 (10)
C50.9789 (5)0.5918 (4)0.3668 (2)0.0212 (10)
C61.0392 (5)0.5747 (4)0.4767 (2)0.0226 (11)
C70.7985 (5)0.5127 (4)0.3104 (2)0.0226 (10)
C80.5578 (5)0.4334 (4)0.1638 (2)0.0240 (10)
C90.4039 (4)0.4350 (4)0.2092 (2)0.0250 (11)
C100.2330 (5)0.3568 (4)0.1612 (2)0.0263 (11)
C110.2161 (5)0.2724 (4)0.0662 (2)0.0273 (11)
C120.3676 (5)0.2727 (4)0.0172 (3)0.0324 (12)
C130.5356 (5)0.3535 (5)0.0654 (2)0.0315 (12)
C141.1767 (5)0.5531 (5)0.7017 (3)0.0370 (13)
C151.6479 (5)0.7425 (5)0.5441 (3)0.0319 (12)
C161.3098 (5)0.8853 (5)0.2132 (3)0.0366 (14)
H41.0439680.6922860.2348450.0286*
H60.9647880.5105970.513410.0271*
H90.4159760.4914630.2754740.03*
H100.1269660.3608180.1932330.0316*
H120.3546530.217079−0.0493980.0389*
H130.6389750.3552150.0312350.0378*
H14a1.2308130.5722640.7764970.0444*
H14b1.0449230.5881520.6820850.0444*
H14c1.1829750.438670.6869180.0444*
H15a1.7537390.8053080.5854710.0382*
H15b1.6432030.6389740.5780740.0382*
H15c1.6645540.7251270.4738440.0382*
H16a1.4016520.9548630.1929560.0439*
H16b1.2992410.7843870.1743830.0439*
H16c1.1868280.9384640.1971260.0439*
H70.7236790.4590980.3518030.0271*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0321 (4)0.0363 (4)0.0337 (4)−0.0062 (4)−0.0049 (3)−0.0031 (4)
O10.0277 (12)0.0274 (12)0.0184 (10)−0.0043 (10)0.0021 (8)−0.0007 (9)
O20.0210 (12)0.0256 (12)0.0276 (11)−0.0031 (9)0.0023 (9)−0.0061 (9)
O30.0298 (13)0.0353 (12)0.0235 (11)−0.0092 (11)0.0054 (10)0.0014 (10)
N10.0248 (16)0.0292 (15)0.0227 (15)−0.0020 (12)0.0032 (12)−0.0012 (11)
C10.0216 (16)0.0189 (14)0.0184 (14)0.0012 (14)0.0039 (11)−0.0004 (13)
C20.0190 (16)0.0203 (15)0.0239 (17)−0.0012 (13)0.0007 (13)−0.0033 (12)
C30.0235 (18)0.0192 (17)0.0280 (17)−0.0008 (13)0.0115 (14)0.0002 (12)
C40.0229 (17)0.0235 (17)0.0235 (15)0.0008 (14)0.0030 (12)0.0005 (13)
C50.0182 (18)0.0199 (15)0.0251 (17)0.0011 (12)0.0046 (14)−0.0007 (12)
C60.0239 (19)0.0209 (17)0.0227 (17)0.0018 (13)0.0057 (13)0.0015 (12)
C70.0211 (17)0.0200 (16)0.0251 (17)−0.0003 (13)0.0033 (13)−0.0005 (13)
C80.0263 (17)0.0220 (16)0.0206 (16)−0.0015 (15)0.0007 (13)−0.0004 (13)
C90.0252 (18)0.0281 (18)0.0201 (16)0.0027 (15)0.0032 (13)0.0004 (13)
C100.0254 (19)0.0296 (18)0.0219 (17)0.0010 (14)0.0024 (13)0.0003 (14)
C110.034 (2)0.0230 (16)0.0191 (16)0.0008 (14)−0.0037 (14)0.0007 (12)
C120.032 (2)0.0353 (19)0.0270 (18)0.0025 (16)0.0020 (15)−0.0050 (14)
C130.032 (2)0.040 (2)0.0226 (17)−0.0018 (16)0.0080 (14)−0.0030 (15)
C140.035 (2)0.048 (2)0.0262 (19)−0.0060 (18)0.0048 (15)0.0083 (16)
C150.0185 (18)0.0334 (18)0.040 (2)0.0021 (15)0.0018 (15)0.0018 (15)
C160.042 (2)0.043 (2)0.0260 (18)−0.0086 (17)0.0097 (16)0.0074 (15)

Geometric parameters (Å, °)

Cl1—C102.708 (3)C7—H70.96
Cl1—C111.732 (3)C8—C91.384 (5)
Cl1—C122.714 (4)C8—C131.406 (5)
O1—C11.362 (3)C9—C101.383 (4)
O1—C141.423 (5)C9—H90.96
O2—C21.379 (4)C10—C111.390 (5)
O2—C151.427 (4)C10—H100.96
O3—C31.375 (4)C11—C121.398 (6)
O3—C161.424 (4)C12—C131.378 (5)
N1—C71.282 (4)C12—H120.96
N1—C81.417 (4)C13—H130.96
C1—C21.397 (5)C14—H14a0.96
C1—C61.397 (4)C14—H14b0.96
C2—C31.395 (4)C14—H14c0.96
C3—C41.390 (4)C15—H15a0.96
C4—C51.398 (5)C15—H15b0.96
C4—H40.96C15—H15c0.96
C5—C61.385 (4)C16—H16a0.96
C5—C71.466 (4)C16—H16b0.96
C6—H60.96C16—H16c0.96
C10—Cl1—C1252.95 (11)C8—C9—H9119.2976
C1—O1—C14117.5 (2)C10—C9—H9119.2983
C2—O2—C15112.4 (3)C9—C10—C11119.5 (3)
C3—O3—C16117.3 (2)C9—C10—H10120.2657
C7—N1—C8117.6 (3)C11—C10—H10120.265
O1—C1—C2115.4 (3)C10—C11—C12120.2 (3)
O1—C1—C6125.5 (3)C11—C12—C13119.5 (3)
C2—C1—C6119.0 (3)C11—C12—H12120.2721
O2—C2—C1119.1 (3)C13—C12—H12120.2719
O2—C2—C3120.3 (3)C8—C13—C12120.9 (4)
C1—C2—C3120.5 (3)C8—C13—H13119.5347
O3—C3—C2114.3 (3)C12—C13—H13119.5353
O3—C3—C4125.1 (3)O1—C14—H14a109.4713
C2—C3—C4120.5 (3)O1—C14—H14b109.4711
C3—C4—C5118.6 (3)O1—C14—H14c109.4713
C3—C4—H4120.6757H14a—C14—H14b109.4712
C5—C4—H4120.6756H14a—C14—H14c109.4714
C4—C5—C6121.2 (3)H14b—C14—H14c109.471
C4—C5—C7120.8 (3)O2—C15—H15a109.4714
C6—C5—C7118.0 (3)O2—C15—H15b109.4711
C1—C6—C5120.1 (3)O2—C15—H15c109.4715
C1—C6—H6119.9695H15a—C15—H15b109.4705
C5—C6—H6119.9698H15a—C15—H15c109.4714
N1—C7—C5123.1 (3)H15b—C15—H15c109.4714
N1—C7—H7118.4336O3—C16—H16a109.4709
C5—C7—H7118.4335O3—C16—H16b109.4714
N1—C8—C9124.2 (3)O3—C16—H16c109.4711
N1—C8—C13117.3 (3)H16a—C16—H16b109.4712
C9—C8—C13118.4 (3)H16a—C16—H16c109.4712
C8—C9—C10121.4 (3)H16b—C16—H16c109.4715

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7···O1i0.962.593.177 (4)119
C7—H7···O2i0.962.513.471 (4)178
C12—H12···N1ii0.962.613.545 (5)164

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2844).

References

  • Akkurt, M., Jarrahpour, A. A., Aye, M., Gençaslan, M. & Büyükgüngör, O. (2008). Acta Cryst. E64, o2175–o2176. [PMC free article] [PubMed]
  • Brandenburg, K. & Putz, H. (2005). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst.36, 1103.
  • Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Kashmiri, M. A., Tahir, M. N., Akhtar, M., Ahmed, M. & Hanif Ch, A. (2008). Acta Cryst. E64, o790. [PMC free article] [PubMed]
  • Khalaji, A. D. & Harrison, W. T. A. (2008). Anal. Sci.24, x3–x4.
  • Khalaji, A. D. & Ng, S. W. (2008). Acta Cryst. E64, o1771. [PMC free article] [PubMed]
  • Khalaji, A. D., Slawin, A. M. Z. & Woollins, J. D. (2007). Acta Cryst. E63, o4257.
  • Khalaji, A. D., Welter, R., Amirnasr, M. & Barry, A. H. (2008). Anal. Sci.24, x139–x140.
  • Oxford Diffraction (2005). CrysAlis CCD Oxford Diffraction Ltd, Oxford, England.
  • Oxford Diffraction (2008). CrysAlis RED Oxford Diffraction Ltd, Oxford, England.
  • Petříček, V., Dušek, M. & Palatinus, L. (2007). JANA2006 Institute of Physics, Praha, Czech Republic.
  • Ren, X.-Y. & Jian, F.-F. (2008). Acta Cryst. E64, o2027. [PMC free article] [PubMed]
  • Zhang, H. (2008). Acta Cryst. E64, o1219. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography