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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3251.
Published online 2009 November 28. doi:  10.1107/S1600536809050144
PMCID: PMC2972081

(E)-3-[(4-Diethyl­amino-2-hydroxy­benzyl­idene)amino]benzonitrile

Abstract

The mol­ecule of the title compound, C18H19N3O, displays a trans configuration with respect to the C=N double bond. There is a strong intra­molecular O—H(...)N hydrogen-bonding inter­action between the hydr­oxy group and imine N atom. The dihedral angle between the aromatic rings is 30.35 (8)°. The crystal packing is stabilized by O—H(...)N links.

Related literature

For the properties of Schiff bases compounds, see: Zhou et al. (2000 [triangle]); Sriram et al. (2006 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o3251-scheme1.jpg

Experimental

Crystal data

  • C18H19N3O
  • M r = 293.36
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3251-efi1.jpg
  • a = 8.411 (6) Å
  • b = 8.519 (6) Å
  • c = 12.906 (9) Å
  • α = 74.17 (4)°
  • β = 79.00 (4)°
  • γ = 64.65 (2)°
  • V = 801.1 (9) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 K
  • 0.20 × 0.20 × 0.10 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.092, T max = 0.182
  • 8686 measured reflections
  • 3620 independent reflections
  • 2592 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.159
  • S = 1.09
  • 3620 reflections
  • 203 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050144/bx2250sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050144/bx2250Isup2.hkl

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

Acknowledgments

This work was supported financially by the Jiangsu Provincial Key Laboratory of Pulp and Paper Science and Technology Foundation (No. 200813).

supplementary crystallographic information

Comment

Schiff bases compounds attract great interest in many fields of chemistry and biochemistry, primarily due to significant pharmacological activities, e.g. anticancer (Zhou et al., 2000), anti-HIV (Sriram et al., 2006). In addition, Schiff base compounds play important role in the development of coordination chemistry related to magnetism and catalysis. As a continue of my works, we here report the synthesis and crystal structure of the title compound, (I).

The molecular structure of (I) of the title compound is shown in Fig. 1. All the bond lengths and angles in the molecules are in the range of normal values (Allen et al., 1987). The molecule displays a trans configuration about the central C11=N2 bond and adopts the phenol-imine tautomeric form, with a strong intramolecular O—H···N hydrogen bonding interaction (Table 1). The dihedral angle between the mean planes of the two aromatic rings is 30.35 (8) ° indicating that the Schiff-base ligand adopts a non-planar conformation. In addition, two methyl groups are positioned to the opposite direction respectively relative to the plane of the adjacent benzene ring. The crystal packing is stabilized by van der Waals interactions.

Experimental

(E)-3-(4-(diethylamino)-2-hydroxybenzylideneamino)benzonitrile was prepared by reflux of a solution mixture containing 4-(diethylamino)-2-hydroxybenzaldehyde (0.996 g, 5 mmol) in ethanol (20 ml) and a solution containing 3-aminobenzonitrile (0.590 g, 5 mmol) in methanol (20 ml). The reaction mixture was stirred for 6 h under reflux, and then cooled to room temperature slowly. The resulting yellow precipitate was filtered off and the crystals of the title compound suitable for X-ray analysis were obtained from acetonitrile solution by slow evaporation

Refinement

H atoms (for OH) were located in a difference Fourier map and refined isotropically. The remailing H atoms were located geometrically and treated as riding atoms with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 Ueq(C) for aromatic H atoms or 1.5 Ueq (C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C18H19N3OZ = 2
Mr = 293.36F(000) = 312
Triclinic, P1Dx = 1.216 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.411 (6) ÅCell parameters from 2426 reflections
b = 8.519 (6) Åθ = 2.3–27.5°
c = 12.906 (9) ŵ = 0.08 mm1
α = 74.17 (4)°T = 293 K
β = 79.00 (4)°Block, yellow
γ = 64.65 (2)°0.20 × 0.20 × 0.10 mm
V = 801.1 (9) Å3

Data collection

Rigaku SCXmini diffractometer3620 independent reflections
Radiation source: fine-focus sealed tube2592 reflections with I > 2σ(I)
graphiteRint = 0.030
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −11→11
Tmin = 0.092, Tmax = 0.182l = −16→16
8686 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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0841P)2] where P = (Fo2 + 2Fc2)/3
3620 reflections(Δ/σ)max < 0.001
203 parametersΔρmax = 0.20 e Å3
1 restraintΔρmin = −0.16 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
C30.2014 (2)1.0630 (2)0.37779 (12)0.0428 (4)
H3A0.08141.11440.39880.051*
O10.24337 (15)0.87525 (17)0.55059 (9)0.0544 (3)
N20.56035 (17)0.63888 (18)0.59125 (10)0.0456 (3)
C10.4976 (2)0.8526 (2)0.42381 (12)0.0417 (4)
C40.2656 (2)1.1212 (2)0.27203 (12)0.0415 (4)
C130.6447 (2)0.4627 (2)0.76732 (12)0.0455 (4)
H13A0.54540.54520.79740.055*
N10.15321 (18)1.24256 (19)0.19656 (10)0.0503 (4)
C20.31405 (19)0.9308 (2)0.45073 (11)0.0396 (4)
C110.6144 (2)0.7100 (2)0.49704 (12)0.0458 (4)
H11A0.73480.66620.47610.055*
C60.5599 (2)0.9187 (2)0.31953 (12)0.0485 (4)
H6A0.68080.87290.30030.058*
C120.6806 (2)0.4883 (2)0.65573 (12)0.0424 (4)
C90.2167 (2)1.3062 (2)0.08716 (13)0.0547 (4)
H9A0.32861.31240.08910.066*
H9B0.13331.42550.05940.066*
C170.8278 (2)0.3586 (2)0.61325 (13)0.0493 (4)
H17A0.85120.37160.53870.059*
C50.4508 (2)1.0469 (2)0.24531 (13)0.0490 (4)
H5A0.49791.08580.17690.059*
C180.7203 (2)0.2892 (2)0.95013 (14)0.0548 (4)
C140.7571 (2)0.3138 (2)0.83397 (12)0.0465 (4)
C150.9066 (2)0.1876 (2)0.79080 (14)0.0511 (4)
H15A0.98280.08950.83580.061*
C7−0.0392 (2)1.3053 (2)0.21951 (13)0.0533 (4)
H7A−0.06771.20980.26780.064*
H7B−0.09281.33570.15270.064*
C160.9387 (2)0.2118 (2)0.68022 (14)0.0524 (4)
H16A1.03660.12780.65020.063*
N30.6938 (2)0.2678 (3)1.04170 (13)0.0772 (5)
C100.2415 (3)1.1884 (3)0.01095 (15)0.0798 (7)
H10A0.28331.2364−0.05980.120*
H10B0.13071.18370.00740.120*
H10C0.32611.07070.03700.120*
C8−0.1160 (3)1.4645 (3)0.27007 (17)0.0716 (6)
H8A−0.24151.49990.28420.107*
H8B−0.09121.56060.22170.107*
H8C−0.06441.43480.33670.107*
H1A0.342 (3)0.773 (4)0.5846 (19)0.109 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C30.0344 (8)0.0488 (9)0.0402 (8)−0.0142 (7)−0.0010 (6)−0.0073 (7)
O10.0396 (6)0.0676 (8)0.0374 (6)−0.0133 (6)0.0027 (5)−0.0001 (5)
N20.0419 (8)0.0490 (8)0.0392 (7)−0.0114 (6)−0.0061 (6)−0.0083 (6)
C10.0373 (8)0.0466 (9)0.0390 (8)−0.0149 (7)−0.0021 (6)−0.0094 (7)
C40.0416 (9)0.0429 (9)0.0383 (8)−0.0158 (7)−0.0052 (6)−0.0064 (6)
C130.0448 (9)0.0481 (9)0.0412 (8)−0.0157 (7)−0.0031 (7)−0.0110 (7)
N10.0456 (7)0.0564 (9)0.0376 (7)−0.0148 (6)−0.0043 (6)−0.0010 (6)
C20.0368 (8)0.0470 (9)0.0343 (7)−0.0168 (7)0.0004 (6)−0.0098 (6)
C110.0369 (8)0.0526 (10)0.0441 (9)−0.0137 (7)−0.0029 (6)−0.0117 (7)
C60.0345 (8)0.0561 (10)0.0461 (9)−0.0145 (7)0.0030 (7)−0.0076 (7)
C120.0408 (8)0.0466 (9)0.0394 (8)−0.0157 (7)−0.0053 (6)−0.0099 (7)
C90.0568 (11)0.0526 (10)0.0429 (9)−0.0192 (8)−0.0063 (7)0.0051 (7)
C170.0516 (10)0.0518 (10)0.0418 (9)−0.0161 (8)−0.0019 (7)−0.0146 (7)
C50.0442 (9)0.0556 (10)0.0408 (8)−0.0203 (8)0.0046 (7)−0.0053 (7)
C180.0590 (11)0.0590 (11)0.0458 (10)−0.0276 (9)−0.0059 (8)−0.0023 (8)
C140.0513 (9)0.0497 (9)0.0415 (8)−0.0251 (8)−0.0050 (7)−0.0056 (7)
C150.0520 (10)0.0435 (9)0.0543 (10)−0.0166 (8)−0.0121 (8)−0.0039 (7)
C70.0477 (8)0.0562 (11)0.0507 (10)−0.0176 (8)−0.0121 (7)−0.0029 (8)
C160.0491 (10)0.0446 (10)0.0585 (11)−0.0124 (8)−0.0015 (8)−0.0159 (8)
N30.0913 (13)0.0963 (14)0.0452 (9)−0.0474 (11)−0.0026 (8)−0.0027 (8)
C100.0944 (17)0.0927 (16)0.0488 (11)−0.0326 (13)−0.0029 (10)−0.0197 (11)
C80.0696 (13)0.0594 (12)0.0721 (13)−0.0158 (10)−0.0011 (10)−0.0126 (10)

Geometric parameters (Å, °)

C3—C21.379 (2)C9—C101.516 (3)
C3—C41.407 (2)C9—H9A0.9700
C3—H3A0.9300C9—H9B0.9700
O1—C21.3616 (19)C17—C161.379 (2)
O1—H1A0.98 (3)C17—H17A0.9300
N2—C111.294 (2)C5—H5A0.9300
N2—C121.410 (2)C18—N31.139 (2)
C1—C61.404 (2)C18—C141.447 (2)
C1—C21.410 (2)C14—C151.396 (2)
C1—C111.428 (2)C15—C161.376 (2)
C4—N11.370 (2)C15—H15A0.9300
C4—C51.420 (2)C7—C81.502 (3)
C13—C141.390 (2)C7—H7A0.9700
C13—C121.390 (2)C7—H7B0.9700
C13—H13A0.9300C16—H16A0.9300
N1—C91.454 (2)C10—H10A0.9600
N1—C71.468 (2)C10—H10B0.9600
C11—H11A0.9300C10—H10C0.9600
C6—C51.363 (2)C8—H8A0.9600
C6—H6A0.9300C8—H8B0.9600
C12—C171.398 (2)C8—H8C0.9600
C2—C3—C4120.82 (15)C16—C17—C12120.98 (15)
C2—C3—H3A119.6C16—C17—H17A119.5
C4—C3—H3A119.6C12—C17—H17A119.5
C2—O1—H1A104.4 (14)C6—C5—C4120.24 (15)
C11—N2—C12120.13 (14)C6—C5—H5A119.9
C6—C1—C2116.50 (14)C4—C5—H5A119.9
C6—C1—C11121.36 (15)N3—C18—C14179.0 (2)
C2—C1—C11122.11 (14)C13—C14—C15121.09 (15)
N1—C4—C3121.23 (15)C13—C14—C18119.75 (16)
N1—C4—C5121.00 (14)C15—C14—C18119.16 (16)
C3—C4—C5117.75 (15)C16—C15—C14118.49 (16)
C14—C13—C12120.03 (15)C16—C15—H15A120.8
C14—C13—H13A120.0C14—C15—H15A120.8
C12—C13—H13A120.0N1—C7—C8112.48 (16)
C4—N1—C9122.17 (15)N1—C7—H7A109.1
C4—N1—C7121.48 (14)C8—C7—H7A109.1
C9—N1—C7116.19 (13)N1—C7—H7B109.1
O1—C2—C3118.17 (14)C8—C7—H7B109.1
O1—C2—C1120.13 (14)H7A—C7—H7B107.8
C3—C2—C1121.70 (14)C15—C16—C17120.95 (16)
N2—C11—C1123.02 (15)C15—C16—H16A119.5
N2—C11—H11A118.5C17—C16—H16A119.5
C1—C11—H11A118.5C9—C10—H10A109.5
C5—C6—C1122.87 (15)C9—C10—H10B109.5
C5—C6—H6A118.6H10A—C10—H10B109.5
C1—C6—H6A118.6C9—C10—H10C109.5
C13—C12—C17118.42 (15)H10A—C10—H10C109.5
C13—C12—N2118.03 (14)H10B—C10—H10C109.5
C17—C12—N2123.44 (14)C7—C8—H8A109.5
N1—C9—C10112.94 (17)C7—C8—H8B109.5
N1—C9—H9A109.0H8A—C8—H8B109.5
C10—C9—H9A109.0C7—C8—H8C109.5
N1—C9—H9B109.0H8A—C8—H8C109.5
C10—C9—H9B109.0H8B—C8—H8C109.5
H9A—C9—H9B107.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···N20.98 (3)1.70 (3)2.607 (3)153 (2)
C16—H16A···O1i0.932.603.504 (3)164

Symmetry codes: (i) x+1, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2250).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sriram, D., Yogeeswari, P., Myneedu, N. S. & Saraswat, V. (2006). Bioorg. Med. Chem. Lett. 16, 2127–2129. [PubMed]
  • Zhou, Y.-S., Zhang, L.-J., Zeng, X.-R., Vittal, J. J. & You, X.-Z. (2000). J. Mol. Struct. 524, 241–250.

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