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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2039.
Published online 2010 July 17. doi:  10.1107/S160053681002742X
PMCID: PMC3007474

N-[(E)-4-Chloro­benzyl­idene]-N′-phenyl­benzene-1,4-diamine

Abstract

The title compound, C19H15ClN2, adopts an E configuration with respect to the position of the chloro­benzene and diphenyl­amine groups on the C=N azomethine bond. The mol­ecule is not planar, the central six-membered ring making angles of 12.26 (10) and 44.18 (11)° with the 4-chloro­phenyl and phenyl rings, respectively. In the crystal structure, weak C—H(...)π inter­actions contribute to the stabilization of the packing.

Related literature

For related structures, see: Ojala et al. (2007 [triangle]); Fun et al. (2008 [triangle]). For standard bond lengths, see: Allen et al. (1987 [triangle]). For the biological activity of Schiff bases, see: Küstü et al. (2007 [triangle]) and for their pharmaceutical properties and applications as corrosion inhibitors, see: Singh & Dhakarey (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2039-scheme1.jpg

Experimental

Crystal data

  • C19H15ClN2
  • M r = 306.78
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2039-efi1.jpg
  • a = 10.3353 (15) Å
  • b = 17.045 (3) Å
  • c = 8.7893 (13) Å
  • β = 97.384 (3)°
  • V = 1535.5 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 298 K
  • 0.50 × 0.39 × 0.12 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.886, T max = 0.971
  • 8939 measured reflections
  • 2860 independent reflections
  • 2076 reflections with I > 2/s(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.127
  • S = 1.05
  • 2860 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 [triangle]) and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002742X/zq2049sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002742X/zq2049Isup2.hkl

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

Acknowledgments

The authors thank the Ministry of Higher Education of Malaysia, Universiti Teknologi MARA and Universiti Kebangsaan Malaysian for the research grants Nos. 600-RMI/ST/FRGS 5/3/Fst(47/2010) and UKM-OUP-BTT-28/2007. NZNH thanks UiTM for the Fellowship Scheme Award.

supplementary crystallographic information

Comment

The continuing study on Schiff bases are driven not only because of their application as ligands but also because of their biological (Singh & Dhakarey, 2009) and pharmaceutical properties and as corrosion inhibitors (Küstü et al., 2007).

The title compound, C19H15N2Cl (I), is a Schiff base having chlorobenzylidene and phenyl groups attached at the terminal nitrogen atoms of the 1,4-diaminobenzene group (Fig.1). The whole molecule is not planar. Each benzene ring is planar with a maximum deviation of 0.011 (2) Å for the C6 atom from the (C1—C6) ring. The middle (C8—C13) ring makes angles of 12.26 (10)° and 44.18 (11)° with the (C1—C6) and (C14—C19) rings, respectively. The dihedral angle between (C1—C6) and (C14—C19) rings is 56.00 (11)°. The E conformation about the C7=N1 double bond is also observed in N,N' -bis(2-methoxybenzylidene)-p-phenylenediamine (II) with an angle of 12.10 (15)° between the mean planes of the benzene rings (Ojala et al., 2007). The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in (II) and 2-{(4-(phenyldiazenyl)phenl]imino-methyl}phenol (Fun et al., 2008).

In the crystal structure, the molecule is stablized by C—H..π interactions, C1—H1B ···Cg3 (C14—C19) and C16—H16A···Cg1 (C1—C6) with H···Cg distances of 2.95 and 2.90 Å, and C—H···Cg angles of 135 and 136°, respectively.

Experimental

4-Chlorobenzaldehyde (0.7029 g, 0.005 mol) in 15 ml of ethanol and N-phenyl-1,4-phenylenediamine (0.9212 g, 0.005 mol) in 10 ml of ethanol were mixed in a round bottom flask. The mixture was stirred for 30 minutes at about 30 °C. The mixture was left to cool down in an ice bath. A green solid was collected and washed with cold ethanol. Green crystals were obtained by recrystallization from toluene (yield 72%; melting point: 408–411 K; CHNS: C, 74.38; H, 4.93; N, 9.13. Found: C, 74.09; H, 4.91; N, 9.08. IR (cm-1): C=N, 1592; N—H, 3408; C—Cl, 749.

Refinement

The H atoms were positioned geometrically with C—H = 0.93 and N—H = 0.86 Å and constrained to ride on their parent atoms with Uiso(H)= 1.2 x Ueq (C or N).

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.

Crystal data

C19H15ClN2F(000) = 640
Mr = 306.78Dx = 1.327 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1956 reflections
a = 10.3353 (15) Åθ = 1.9–25.5°
b = 17.045 (3) ŵ = 0.25 mm1
c = 8.7893 (13) ÅT = 298 K
β = 97.384 (3)°Block, colourless
V = 1535.5 (4) Å30.50 × 0.39 × 0.12 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer2860 independent reflections
Radiation source: fine-focus sealed tube2076 reflections with I > 2/s(I)
graphiteRint = 0.038
Detector resolution: 83.66 pixels mm-1θmax = 25.5°, θmin = 1.9°
ω scanh = −11→12
Absorption correction: multi-scan (SADABS; Bruker, 2000)k = −14→20
Tmin = 0.886, Tmax = 0.971l = −10→9
8939 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0491P)2 + 0.388P] where P = (Fo2 + 2Fc2)/3
2860 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.27 e Å3

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
Cl10.49291 (8)0.14092 (4)1.51538 (8)0.0878 (3)
N10.19891 (17)0.12993 (11)0.7853 (2)0.0563 (5)
N2−0.00657 (18)0.08239 (12)0.1689 (2)0.0649 (6)
H2A0.03630.04920.12120.078*
C10.3831 (2)0.03701 (13)1.1159 (3)0.0595 (6)
H1B0.3918−0.01231.07300.071*
C20.4384 (2)0.05077 (14)1.2645 (3)0.0614 (6)
H2B0.48510.01161.32100.074*
C30.4233 (2)0.12328 (14)1.3281 (3)0.0568 (6)
C40.3532 (2)0.18165 (13)1.2465 (3)0.0583 (6)
H4A0.34210.23011.29150.070*
C50.2997 (2)0.16732 (13)1.0975 (3)0.0540 (6)
H5A0.25260.20671.04180.065*
C60.3150 (2)0.09492 (13)1.0290 (2)0.0502 (5)
C70.2607 (2)0.07919 (13)0.8699 (3)0.0556 (6)
H7A0.27230.02960.82960.067*
C80.1486 (2)0.11346 (13)0.6310 (2)0.0506 (5)
C90.0617 (2)0.16743 (13)0.5585 (3)0.0565 (6)
H9A0.03880.21100.61300.068*
C100.0079 (2)0.15853 (13)0.4074 (3)0.0574 (6)
H10A−0.04970.19600.36150.069*
C110.0396 (2)0.09396 (13)0.3239 (3)0.0514 (5)
C120.1269 (2)0.03969 (14)0.3963 (3)0.0575 (6)
H12A0.1493−0.00400.34180.069*
C130.1808 (2)0.04887 (13)0.5455 (3)0.0561 (6)
H13A0.23950.01170.59070.067*
C14−0.1137 (2)0.11789 (12)0.0811 (3)0.0500 (5)
C15−0.2251 (2)0.13990 (12)0.1426 (3)0.0532 (6)
H15A−0.22970.13310.24680.064*
C16−0.3291 (2)0.17186 (13)0.0496 (3)0.0581 (6)
H16A−0.40320.18710.09200.070*
C17−0.3251 (2)0.18156 (14)−0.1047 (3)0.0649 (6)
H17A−0.39570.2034−0.16670.078*
C18−0.2160 (3)0.15871 (14)−0.1662 (3)0.0650 (6)
H18A−0.21330.1642−0.27100.078*
C19−0.1107 (2)0.12777 (14)−0.0752 (3)0.0592 (6)
H19A−0.03680.1133−0.11850.071*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.1158 (6)0.0755 (5)0.0653 (4)−0.0226 (4)−0.0141 (4)0.0041 (3)
N10.0524 (11)0.0529 (11)0.0630 (12)0.0028 (9)0.0051 (9)−0.0015 (10)
N20.0588 (12)0.0757 (14)0.0600 (12)0.0135 (10)0.0066 (10)−0.0130 (10)
C10.0701 (15)0.0421 (12)0.0673 (16)0.0003 (11)0.0133 (12)0.0000 (11)
C20.0662 (15)0.0529 (14)0.0643 (15)0.0013 (12)0.0057 (12)0.0133 (12)
C30.0604 (14)0.0540 (14)0.0555 (14)−0.0116 (11)0.0057 (11)0.0039 (11)
C40.0668 (15)0.0431 (13)0.0659 (15)−0.0022 (11)0.0121 (12)−0.0037 (11)
C50.0508 (13)0.0477 (13)0.0633 (14)0.0054 (10)0.0072 (11)0.0043 (11)
C60.0457 (12)0.0469 (13)0.0594 (14)−0.0024 (10)0.0116 (10)0.0018 (11)
C70.0589 (14)0.0455 (13)0.0628 (15)−0.0044 (11)0.0092 (11)−0.0050 (11)
C80.0451 (12)0.0494 (13)0.0573 (14)−0.0045 (10)0.0066 (10)−0.0005 (10)
C90.0581 (14)0.0464 (13)0.0653 (15)0.0028 (11)0.0083 (11)−0.0064 (11)
C100.0578 (14)0.0478 (13)0.0645 (15)0.0046 (11)0.0005 (11)0.0023 (11)
C110.0426 (12)0.0540 (14)0.0583 (14)−0.0037 (10)0.0091 (10)−0.0028 (11)
C120.0481 (13)0.0568 (14)0.0677 (15)0.0041 (11)0.0082 (11)−0.0126 (12)
C130.0460 (12)0.0538 (14)0.0681 (15)0.0056 (11)0.0056 (11)−0.0019 (12)
C140.0481 (12)0.0453 (12)0.0562 (13)−0.0049 (10)0.0052 (10)−0.0059 (10)
C150.0550 (13)0.0522 (13)0.0535 (13)−0.0032 (11)0.0119 (10)−0.0031 (10)
C160.0528 (13)0.0527 (14)0.0691 (16)0.0027 (11)0.0087 (11)−0.0079 (12)
C170.0684 (16)0.0557 (14)0.0676 (16)0.0073 (12)−0.0033 (13)−0.0016 (12)
C180.0788 (17)0.0640 (16)0.0519 (14)−0.0021 (13)0.0072 (12)−0.0003 (12)
C190.0574 (14)0.0626 (15)0.0603 (15)−0.0054 (12)0.0175 (11)−0.0071 (12)

Geometric parameters (Å, °)

Cl1—C31.736 (2)C9—C101.381 (3)
N1—C71.260 (3)C9—H9A0.9300
N1—C81.417 (3)C10—C111.385 (3)
N2—C111.399 (3)C10—H10A0.9300
N2—C141.402 (3)C11—C121.388 (3)
N2—H2A0.8600C12—C131.367 (3)
C1—C21.377 (3)C12—H12A0.9300
C1—C61.384 (3)C13—H13A0.9300
C1—H1B0.9300C14—C151.385 (3)
C2—C31.373 (3)C14—C191.389 (3)
C2—H2B0.9300C15—C161.376 (3)
C3—C41.377 (3)C15—H15A0.9300
C4—C51.376 (3)C16—C171.373 (3)
C4—H4A0.9300C16—H16A0.9300
C5—C61.391 (3)C17—C181.368 (3)
C5—H5A0.9300C17—H17A0.9300
C6—C71.463 (3)C18—C191.370 (3)
C7—H7A0.9300C18—H18A0.9300
C8—C91.382 (3)C19—H19A0.9300
C8—C131.397 (3)
C7—N1—C8121.7 (2)C9—C10—C11120.2 (2)
C11—N2—C14128.39 (19)C9—C10—H10A119.9
C11—N2—H2A115.8C11—C10—H10A119.9
C14—N2—H2A115.8C10—C11—C12118.1 (2)
C2—C1—C6121.4 (2)C10—C11—N2123.6 (2)
C2—C1—H1B119.3C12—C11—N2118.2 (2)
C6—C1—H1B119.3C13—C12—C11121.6 (2)
C3—C2—C1119.0 (2)C13—C12—H12A119.2
C3—C2—H2B120.5C11—C12—H12A119.2
C1—C2—H2B120.5C12—C13—C8120.7 (2)
C2—C3—C4121.2 (2)C12—C13—H13A119.6
C2—C3—Cl1119.14 (19)C8—C13—H13A119.6
C4—C3—Cl1119.66 (19)C15—C14—C19118.6 (2)
C5—C4—C3119.2 (2)C15—C14—N2122.7 (2)
C5—C4—H4A120.4C19—C14—N2118.7 (2)
C3—C4—H4A120.4C16—C15—C14120.0 (2)
C4—C5—C6121.0 (2)C16—C15—H15A120.0
C4—C5—H5A119.5C14—C15—H15A120.0
C6—C5—H5A119.5C17—C16—C15121.0 (2)
C1—C6—C5118.2 (2)C17—C16—H16A119.5
C1—C6—C7120.1 (2)C15—C16—H16A119.5
C5—C6—C7121.7 (2)C18—C17—C16119.1 (2)
N1—C7—C6122.8 (2)C18—C17—H17A120.4
N1—C7—H7A118.6C16—C17—H17A120.4
C6—C7—H7A118.6C17—C18—C19120.8 (2)
C9—C8—C13117.5 (2)C17—C18—H18A119.6
C9—C8—N1116.5 (2)C19—C18—H18A119.6
C13—C8—N1126.0 (2)C18—C19—C14120.5 (2)
C10—C9—C8121.8 (2)C18—C19—H19A119.8
C10—C9—H9A119.1C14—C19—H19A119.8
C8—C9—H9A119.1
C6—C1—C2—C31.1 (4)C9—C10—C11—N2−177.3 (2)
C1—C2—C3—C40.7 (4)C14—N2—C11—C10−18.4 (4)
C1—C2—C3—Cl1−179.97 (17)C14—N2—C11—C12164.8 (2)
C2—C3—C4—C5−1.4 (3)C10—C11—C12—C130.1 (3)
Cl1—C3—C4—C5179.28 (17)N2—C11—C12—C13177.0 (2)
C3—C4—C5—C60.3 (3)C11—C12—C13—C80.5 (3)
C2—C1—C6—C5−2.1 (3)C9—C8—C13—C12−0.5 (3)
C2—C1—C6—C7178.2 (2)N1—C8—C13—C12−179.1 (2)
C4—C5—C6—C11.4 (3)C11—N2—C14—C15−32.5 (3)
C4—C5—C6—C7−178.9 (2)C11—N2—C14—C19150.9 (2)
C8—N1—C7—C6179.28 (18)C19—C14—C15—C16−0.9 (3)
C1—C6—C7—N1−179.3 (2)N2—C14—C15—C16−177.6 (2)
C5—C6—C7—N11.0 (3)C14—C15—C16—C170.8 (3)
C7—N1—C8—C9167.8 (2)C15—C16—C17—C180.2 (4)
C7—N1—C8—C13−13.6 (3)C16—C17—C18—C19−1.2 (4)
C13—C8—C9—C100.1 (3)C17—C18—C19—C141.0 (4)
N1—C8—C9—C10178.8 (2)C15—C14—C19—C180.0 (3)
C8—C9—C10—C110.5 (3)N2—C14—C19—C18176.8 (2)
C9—C10—C11—C12−0.6 (3)

Hydrogen-bond geometry (Å, °)

Cg1 and Cg3 are the centroids of the C1–C6 and C14–C19 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C1—H1B···Cg3i0.932.953.661 (2)135
C16—H16A···Cg1ii0.932.903.624 (2)136

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2049).

References

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  • Bruker (2000). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fun, H.-K., Kargar, H. & Kia, R. (2008). Acta Cryst. E64, o1308. [PMC free article] [PubMed]
  • Küstü, C., Emregül, K. C. & Atakol, O. (2007). Corros. Sci. pp. 2800–2814.
  • Nardelli, M. (1995). J. Appl. Cryst.28, 659.
  • Ojala, W. H., Arola, T. M., Herrera, N., Balidemaj, B. & Ojala, C. R. (2007). Acta Cryst. C63, o207–o211. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Singh, P. & Dhakarey, R. K. S. (2009). Rasayan J. Chem.2, 869–874.
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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