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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o362.
Published online 2009 January 23. doi:  10.1107/S1600536809001871
PMCID: PMC2968393

(E)-4-Chloro-N-[(E)-2-methyl-3-phenyl­allyl­idene]aniline

Abstract

The title Schiff base compound, C16H14ClN, adopts E configurations with respect to both the C=C and C=N bonds. The dihedral angle between the two aromatic rings is 53.27 (4)°, while the plane through the C=C—C=N system is inclined at 9.06 (8)° to the benzene ring and 44.92 (5)° to the chloro­benzene ring. In the crystal structure, weak C—H(...)Cl and C—H(...)N hydrogen bonds stack the mol­ecules down the a axis.

Related literature

For background to the use of Schiff bases as ligands see: Khalaji et al. (2008a [triangle],b [triangle]); and for their bio-activity, see: Karthikeyan et al. (2006 [triangle]); Xiong et al. (2008 [triangle]); Sriram et al. (2006 [triangle]). For related structures, see: Khalaji et al. (2007 [triangle]); Khalaji & Harrison (2008 [triangle]); Khalaji et al. (2008c [triangle]). For reference structural data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-0o362-scheme1.jpg

Experimental

Crystal data

  • C16H14ClN
  • M r = 255.73
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o362-efi1.jpg
  • a = 7.2486 (10) Å
  • b = 11.6637 (17) Å
  • c = 15.598 (2) Å
  • V = 1318.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 89 (2) K
  • 0.36 × 0.24 × 0.03 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2006 [triangle]) T min = 0.841, T max = 0.992
  • 21077 measured reflections
  • 4077 independent reflections
  • 3517 reflections with I > 2σ(I)
  • R int = 0.058

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.109
  • S = 1.06
  • 4077 reflections
  • 164 parameters
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.36 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1742 Friedel pairs
  • Flack parameter: 0.01 (6)

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: APEX2 and SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]) and TITAN (Hunter & Simpson, 1999 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 [triangle]), PLATON (Spek, 2003 [triangle]) and publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001871/pk2147sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001871/pk2147Isup2.hkl

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

Acknowledgments

We thank the University of Otago for purchase of the diffractometer.

supplementary crystallographic information

Comment

Schiff-bases are well known chelating ligands in coordination chemistry (Khalaji et al., 2008a,b), and exhibit a wide range of biological activities (Karthikeyan et al., 2006) including anti-HIV activity (Xiong et al., 2008; Sriram et al., 2006). As a continuation of our work on the synthesis and structural characterization of Schiff-base compounds (Khalaji et al., 2007; Khalaji & Harrison, 2008; Khalaji et al., 2008c), we report here the structure of the title compound, C16H14NCl, (I), Fig 1.

The title Schiff-base compound, C16H14NCl, adopts E configurations with respect to both the C2=C4 and C1=N1 bonds. Bond lengths in the molecule are normal (Allen, et al., 1987) and similar to those found in related compounds (Khalaji et al., 2007; Khalaji & Harrison, 2008; Khalaji et al., 2008c). The dihedral angle between the two aromatic rings is 53.27 (4)° while the plane through the C2=C4–C1=N1 system is inclined at 9.06 (8)° to the C5···C10 ring and 44.92 (5)° to the C11···C16 ring.

In the crystal structure, weak C13—H13···Cl1 and C7—H7···N1 hydrogen bonds stack the molecules down the a axis.

Experimental

The title compound was prepared in 76% yield from 4-chloroaniline and α-methylcinnamaldehyde as reported elsewhere (Khalaji et al. 2007) and recrystallized from methanol.

Refinement

The H atom bound to N1 was located in a difference electron density map and refined freely with an isotropic displacement parameter. All other H-atoms were refined using a riding model with d(C—H) = 0.95 Å, Uiso= 1.2Ueq (C) for aromatic and 0.98 Å, Uiso = 1.5Ueq (C) for CH3 H atoms.

Figures

Fig. 1.
The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
Fig. 2.
Crystal packing of (I) viewed down the a axis with hydrogen bonds drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

Crystal data

C16H14ClNF(000) = 536
Mr = 255.73Dx = 1.288 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5396 reflections
a = 7.2486 (10) Åθ = 2.6–28.8°
b = 11.6637 (17) ŵ = 0.27 mm1
c = 15.598 (2) ÅT = 89 K
V = 1318.7 (3) Å3Rectangular plate, pale yellow
Z = 40.36 × 0.24 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer4077 independent reflections
Radiation source: fine-focus sealed tube3517 reflections with I > 2σ(I)
graphiteRint = 0.058
ω scansθmax = 30.7°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −10→10
Tmin = 0.841, Tmax = 0.992k = −16→16
21077 measured reflectionsl = −21→22

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.109w = 1/[σ2(Fo2) + (0.0649P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
4077 reflectionsΔρmax = 0.30 e Å3
164 parametersΔρmin = −0.36 e Å3
0 restraintsAbsolute structure: Flack (1983), 1742 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (6)

Special details

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.

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

xyzUiso*/Ueq
N10.5152 (2)0.52967 (12)0.68870 (9)0.0202 (3)
C10.4972 (2)0.61272 (13)0.63497 (9)0.0183 (3)
H10.45500.68480.65530.022*
C20.5394 (2)0.60026 (13)0.54384 (9)0.0172 (3)
C30.6040 (3)0.48397 (13)0.51348 (10)0.0224 (3)
H3A0.53030.46010.46390.034*
H3B0.58920.42800.55980.034*
H3C0.73430.48840.49700.034*
C40.5161 (2)0.69557 (13)0.49535 (10)0.0178 (3)
H40.47250.76020.52640.021*
C50.5458 (2)0.71712 (13)0.40389 (10)0.0166 (3)
C60.6332 (3)0.64156 (14)0.34605 (10)0.0227 (3)
H60.67710.56950.36590.027*
C70.6560 (2)0.67119 (14)0.26031 (10)0.0228 (3)
H70.71510.61920.22230.027*
C80.5931 (2)0.77606 (14)0.22974 (10)0.0228 (3)
H80.60720.79530.17090.027*
C90.5089 (3)0.85283 (15)0.28615 (11)0.0243 (4)
H90.46720.92520.26600.029*
C100.4861 (2)0.82324 (14)0.37165 (10)0.0205 (3)
H100.42860.87620.40940.025*
C110.4819 (2)0.55276 (13)0.77639 (10)0.0182 (3)
C120.5526 (2)0.64996 (13)0.81773 (10)0.0203 (3)
H120.62330.70400.78620.024*
C130.5200 (2)0.66792 (13)0.90454 (10)0.0207 (3)
H130.56710.73420.93230.025*
C140.4183 (2)0.58807 (13)0.94995 (10)0.0193 (3)
Cl10.38085 (6)0.60910 (4)1.05938 (2)0.02595 (11)
C150.3494 (2)0.48964 (13)0.91081 (11)0.0206 (3)
H150.28000.43540.94280.025*
C160.3841 (2)0.47222 (13)0.82400 (10)0.0199 (3)
H160.34040.40450.79690.024*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0204 (7)0.0212 (6)0.0190 (6)0.0000 (5)0.0007 (5)0.0002 (5)
C10.0174 (7)0.0186 (6)0.0189 (7)0.0011 (6)0.0001 (6)−0.0018 (6)
C20.0162 (7)0.0171 (6)0.0182 (7)0.0014 (6)−0.0009 (5)−0.0021 (6)
C30.0278 (9)0.0173 (6)0.0222 (8)0.0029 (7)0.0032 (7)−0.0004 (6)
C40.0186 (8)0.0163 (7)0.0185 (7)0.0000 (6)0.0011 (6)−0.0038 (5)
C50.0145 (7)0.0161 (6)0.0191 (7)−0.0025 (6)0.0003 (6)−0.0018 (5)
C60.0291 (9)0.0164 (6)0.0225 (8)0.0000 (7)0.0035 (7)−0.0014 (5)
C70.0280 (9)0.0206 (7)0.0199 (7)−0.0031 (7)0.0053 (6)−0.0036 (6)
C80.0244 (9)0.0264 (7)0.0175 (7)−0.0045 (7)−0.0010 (6)0.0008 (6)
C90.0257 (9)0.0238 (7)0.0233 (8)0.0035 (7)0.0006 (7)0.0054 (6)
C100.0204 (8)0.0198 (7)0.0213 (7)0.0028 (6)0.0019 (6)0.0004 (6)
C110.0174 (7)0.0190 (7)0.0183 (7)0.0034 (6)−0.0007 (6)0.0014 (6)
C120.0209 (8)0.0183 (6)0.0218 (7)−0.0003 (6)−0.0028 (6)0.0042 (6)
C130.0233 (8)0.0174 (7)0.0214 (7)−0.0008 (6)−0.0039 (6)−0.0012 (6)
C140.0181 (7)0.0217 (7)0.0180 (7)0.0051 (6)−0.0004 (6)0.0021 (6)
Cl10.0302 (2)0.02978 (19)0.01791 (17)0.00604 (18)0.00123 (15)−0.00069 (15)
C150.0197 (8)0.0196 (7)0.0225 (7)0.0009 (6)0.0016 (6)0.0030 (6)
C160.0199 (8)0.0172 (6)0.0228 (7)0.0000 (6)−0.0005 (6)−0.0006 (6)

Geometric parameters (Å, °)

N1—C11.287 (2)C8—C91.396 (2)
N1—C111.415 (2)C8—H80.9500
C1—C21.4612 (19)C9—C101.387 (2)
C1—H10.9500C9—H90.9500
C2—C41.355 (2)C10—H100.9500
C2—C31.511 (2)C11—C161.392 (2)
C3—H3A0.9800C11—C121.401 (2)
C3—H3B0.9800C12—C131.390 (2)
C3—H3C0.9800C12—H120.9500
C4—C51.464 (2)C13—C141.383 (2)
C4—H40.9500C13—H130.9500
C5—C101.404 (2)C14—C151.393 (2)
C5—C61.412 (2)C14—Cl11.7456 (16)
C6—C71.391 (2)C15—C161.392 (2)
C6—H60.9500C15—H150.9500
C7—C81.390 (2)C16—H160.9500
C7—H70.9500
C1—N1—C11117.96 (14)C7—C8—H8120.3
N1—C1—C2122.50 (14)C9—C8—H8120.3
N1—C1—H1118.8C10—C9—C8119.89 (15)
C2—C1—H1118.8C10—C9—H9120.1
C4—C2—C1115.80 (14)C8—C9—H9120.1
C4—C2—C3126.88 (13)C9—C10—C5121.79 (15)
C1—C2—C3117.32 (13)C9—C10—H10119.1
C2—C3—H3A109.5C5—C10—H10119.1
C2—C3—H3B109.5C16—C11—C12119.14 (15)
H3A—C3—H3B109.5C16—C11—N1118.32 (14)
C2—C3—H3C109.5C12—C11—N1122.44 (15)
H3A—C3—H3C109.5C13—C12—C11120.52 (15)
H3B—C3—H3C109.5C13—C12—H12119.7
C2—C4—C5131.77 (14)C11—C12—H12119.7
C2—C4—H4114.1C14—C13—C12119.20 (15)
C5—C4—H4114.1C14—C13—H13120.4
C10—C5—C6117.38 (14)C12—C13—H13120.4
C10—C5—C4117.05 (14)C13—C14—C15121.45 (15)
C6—C5—C4125.55 (14)C13—C14—Cl1119.28 (12)
C7—C6—C5120.84 (15)C15—C14—Cl1119.25 (12)
C7—C6—H6119.6C16—C15—C14118.82 (15)
C5—C6—H6119.6C16—C15—H15120.6
C8—C7—C6120.63 (15)C14—C15—H15120.6
C8—C7—H7119.7C11—C16—C15120.83 (14)
C6—C7—H7119.7C11—C16—H16119.6
C7—C8—C9119.46 (15)C15—C16—H16119.6

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7···N1i0.952.673.524 (2)150
C13—H13···Cl1ii0.952.923.7311 (17)144

Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1/2, −y+3/2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2147).

References

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