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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o344.
Published online 2009 January 17. doi:  10.1107/S1600536809000853
PMCID: PMC2968211

4-[4-(4-Nitro­phenyl­diazen­yl)phen­yl]hexa­nenitrile

Abstract

In the mol­ecule of the title compound, C18H18N4O2, the aromatic rings are oriented at a dihedral angle of 3.72 (3)°. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds link the mol­ecules into centrosymmetric dimers. There are also C—H(...)π inter­actions.

Related literature

For general background, see: Bach et al. (1996 [triangle]); Clark & Hester (1991 [triangle]); Taniike et al. (1996 [triangle]). For a related structure, see: Zhao et al. (2002 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-0o344-scheme1.jpg

Experimental

Crystal data

  • C18H18N4O2
  • M r = 322.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o344-efi1.jpg
  • a = 20.113 (4) Å
  • b = 10.590 (2) Å
  • c = 7.6820 (15) Å
  • β = 94.78 (3)°
  • V = 1630.5 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.964, T max = 0.991
  • 3037 measured reflections
  • 2951 independent reflections
  • 1336 reflections with I > 2σ(I)
  • R int = 0.061
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.072
  • wR(F 2) = 0.185
  • S = 0.98
  • 2951 reflections
  • 199 parameters
  • 62 restraints
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks D, I. DOI: 10.1107/S1600536809000853/hk2611sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000853/hk2611Isup2.hkl

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

supplementary crystallographic information

Comment

The photophysical properties of azo compounds are of large interest in the development of nonlinear optical and optical data storage materials (Bach et al., 1996; Taniike et al., 1996; Clark & Hester, 1991). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C7-C12) and B (C13-C18) are, of course, planar, and they are oriented at a dihedral angle of 3.72 (3)°.

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure. There also exist C–H···π interactions (Table 1).

Experimental

The title compound has been synthesized according to a literature method (Zhao et al., 2002). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C18H18N4O2F(000) = 680
Mr = 322.36Dx = 1.313 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 20.113 (4) Åθ = 9–13°
b = 10.590 (2) ŵ = 0.09 mm1
c = 7.6820 (15) ÅT = 293 K
β = 94.78 (3)°Block, red
V = 1630.5 (6) Å30.30 × 0.20 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer1336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.061
graphiteθmax = 25.3°, θmin = 1.0°
ω/2θ scansh = 0→24
Absorption correction: ψ scan (North et al., 1968)k = 0→12
Tmin = 0.964, Tmax = 0.991l = −9→9
3037 measured reflections3 standard reflections every 200 reflections
2951 independent reflections intensity decay: 1%

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)] = 0.072Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.185H-atom parameters constrained
S = 0.98w = 1/[σ2(Fo2) + (0.060P)2 + 1.P] where P = (Fo2 + 2Fc2)/3
2951 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.32 e Å3
62 restraintsΔρmin = −0.37 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N10.4653 (3)−0.1899 (5)0.4255 (7)0.1057 (17)
C10.4327 (3)−0.1281 (7)0.4966 (8)0.107 (2)
O1−0.27421 (18)0.0779 (4)0.7659 (5)0.0975 (13)
O2−0.25317 (17)0.2141 (3)0.9614 (5)0.0828 (11)
N20.07709 (17)0.1393 (3)0.8661 (4)0.0479 (7)
N30.03734 (18)0.0691 (3)0.7775 (4)0.0506 (9)
N4−0.2356 (2)0.1355 (4)0.8566 (6)0.0658 (11)
C20.3903 (2)−0.0199 (5)0.5602 (7)0.0829 (10)
H2B0.41420.05970.56070.099*
H2C0.3493−0.01130.48530.099*
C30.3747 (2)−0.0512 (5)0.7350 (7)0.0829 (10)
H3B0.4143−0.08220.80220.099*
H3C0.3411−0.11710.73090.099*
C40.4104 (3)0.0772 (6)1.1039 (8)0.105 (2)
H4A0.44470.12281.17190.157*
H4B0.4239−0.00911.09200.157*
H4C0.36980.08011.16130.157*
C50.3989 (2)0.1368 (5)0.9246 (7)0.0808 (17)
H5A0.38510.22400.93600.097*
H5B0.44000.13580.86710.097*
C60.3485 (2)0.0682 (5)0.8228 (7)0.0829 (10)
H6A0.35200.12080.71900.099*
C70.2832 (2)0.0858 (4)0.8230 (6)0.0583 (12)
C80.2566 (2)0.1767 (4)0.9332 (5)0.0519 (11)
H8A0.28570.22811.00170.062*
C90.1910 (2)0.1910 (4)0.9421 (5)0.0504 (11)
H9A0.17630.25211.01690.060*
C100.1431 (2)0.1179 (4)0.8435 (5)0.0479 (7)
C110.1685 (2)0.0266 (4)0.7336 (5)0.0498 (11)
H11A0.1390−0.02630.66870.060*
C120.2337 (2)0.0142 (4)0.7206 (5)0.0506 (11)
H12A0.2479−0.04390.64080.061*
C13−0.0292 (2)0.0918 (4)0.8074 (5)0.0470 (10)
C14−0.0524 (2)0.1820 (4)0.9173 (5)0.0511 (11)
H14A−0.02230.23520.97980.061*
C15−0.1198 (2)0.1937 (4)0.9352 (6)0.0588 (12)
H15A−0.13480.25401.01080.071*
C16−0.1639 (2)0.1184 (4)0.8440 (5)0.0521 (11)
C17−0.1442 (2)0.0243 (4)0.7373 (6)0.0583 (12)
H17A−0.1753−0.02890.67830.070*
C18−0.0770 (2)0.0112 (4)0.7203 (5)0.0618 (12)
H18A−0.0627−0.05280.64930.074*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.100 (4)0.112 (4)0.104 (4)0.046 (3)0.004 (3)−0.022 (3)
C10.064 (4)0.138 (6)0.118 (5)0.009 (4)0.005 (3)−0.064 (5)
O10.058 (2)0.128 (3)0.105 (3)−0.018 (2)−0.005 (2)0.007 (3)
O20.073 (2)0.077 (3)0.101 (3)0.017 (2)0.022 (2)0.008 (2)
N20.0573 (17)0.0468 (16)0.0392 (14)0.0041 (14)0.0020 (13)0.0020 (13)
N30.060 (2)0.049 (2)0.043 (2)0.0021 (18)−0.0003 (17)0.0016 (17)
N40.060 (3)0.061 (3)0.076 (3)0.004 (2)0.004 (2)0.023 (2)
C20.069 (2)0.093 (2)0.086 (2)−0.0043 (17)−0.0003 (17)−0.010 (2)
C30.069 (2)0.093 (2)0.086 (2)−0.0043 (17)−0.0003 (17)−0.010 (2)
C40.086 (4)0.112 (5)0.111 (5)−0.048 (4)−0.023 (4)0.008 (4)
C50.042 (3)0.110 (4)0.091 (4)−0.014 (3)0.010 (3)−0.046 (4)
C60.069 (2)0.093 (2)0.086 (2)−0.0043 (17)−0.0003 (17)−0.010 (2)
C70.051 (3)0.069 (3)0.055 (3)−0.007 (2)−0.001 (2)−0.017 (2)
C80.055 (3)0.040 (2)0.061 (3)−0.007 (2)0.006 (2)−0.019 (2)
C90.064 (3)0.047 (3)0.041 (2)−0.001 (2)0.011 (2)−0.014 (2)
C100.0573 (17)0.0468 (16)0.0392 (14)0.0041 (14)0.0020 (13)0.0020 (13)
C110.052 (3)0.052 (3)0.044 (2)0.003 (2)−0.003 (2)−0.005 (2)
C120.056 (3)0.044 (2)0.052 (3)−0.001 (2)0.000 (2)−0.016 (2)
C130.059 (3)0.044 (2)0.038 (2)0.005 (2)0.0057 (19)0.0108 (19)
C140.054 (3)0.051 (3)0.048 (3)0.006 (2)−0.002 (2)−0.005 (2)
C150.070 (3)0.056 (3)0.051 (3)0.012 (2)0.005 (2)−0.005 (2)
C160.065 (3)0.048 (3)0.044 (2)0.002 (2)0.007 (2)0.014 (2)
C170.057 (3)0.058 (3)0.058 (3)−0.005 (2)−0.005 (2)0.003 (2)
C180.075 (3)0.066 (3)0.045 (2)0.001 (3)0.003 (2)−0.007 (2)

Geometric parameters (Å, °)

N1—C11.102 (6)C6—H6A0.9800
C1—C21.533 (7)C7—C81.416 (5)
O1—N41.171 (5)C7—C121.434 (5)
O2—N41.230 (5)C8—C91.334 (5)
N2—N31.251 (4)C8—H8A0.9300
N2—C101.371 (5)C9—C101.407 (5)
N3—C131.398 (5)C9—H9A0.9300
N4—C161.464 (6)C10—C111.407 (5)
C2—C31.443 (6)C11—C121.330 (5)
C2—H2B0.9700C11—H11A0.9300
C2—H2C0.9700C12—H12A0.9300
C3—C61.546 (7)C13—C141.381 (5)
C3—H3B0.9700C13—C181.412 (6)
C3—H3C0.9700C14—C151.379 (5)
C4—C51.515 (7)C14—H14A0.9300
C4—H4A0.9600C15—C161.346 (6)
C4—H4B0.9600C15—H15A0.9300
C4—H4C0.9600C16—C171.369 (6)
C5—C61.427 (6)C17—C181.376 (6)
C5—H5A0.9700C17—H17A0.9300
C5—H5B0.9700C18—H18A0.9300
C6—C71.326 (6)
N1—C1—C2166.2 (8)C6—C7—C8121.3 (4)
N3—N2—C10114.5 (3)C6—C7—C12124.6 (4)
N2—N3—C13112.7 (3)C8—C7—C12114.0 (4)
O1—N4—O2122.0 (5)C9—C8—C7122.1 (4)
O1—N4—C16120.3 (5)C9—C8—H8A118.9
O2—N4—C16117.7 (5)C7—C8—H8A118.9
C3—C2—C1107.1 (5)C8—C9—C10123.1 (4)
C3—C2—H2B110.0C8—C9—H9A118.4
C1—C2—H2B111.2C10—C9—H9A118.4
C3—C2—H2C109.5N2—C10—C9117.9 (4)
C1—C2—H2C110.4N2—C10—C11126.4 (4)
H2B—C2—H2C108.6C9—C10—C11115.7 (4)
C2—C3—C6109.1 (5)C12—C11—C10121.5 (4)
C2—C3—H3B109.9C12—C11—H11A119.2
C6—C3—H3B109.9C10—C11—H11A119.2
C2—C3—H3C109.9C11—C12—C7123.4 (4)
C6—C3—H3C109.9C11—C12—H12A118.3
H3B—C3—H3C108.3C7—C12—H12A118.3
C5—C4—H4A109.5C14—C13—N3126.6 (4)
C5—C4—H4B109.5C14—C13—C18117.2 (4)
H4A—C4—H4B109.5N3—C13—C18116.2 (4)
C5—C4—H4C109.5C15—C14—C13120.5 (4)
H4A—C4—H4C109.5C15—C14—H14A119.7
H4B—C4—H4C109.5C13—C14—H14A119.7
C6—C5—C4109.5 (5)C16—C15—C14120.3 (4)
C6—C5—H5A109.8C16—C15—H15A119.8
C4—C5—H5A109.8C14—C15—H15A119.8
C6—C5—H5B109.8C15—C16—C17122.1 (4)
C4—C5—H5B109.8C15—C16—N4120.1 (4)
H5A—C5—H5B108.2C17—C16—N4117.7 (4)
C7—C6—C5125.9 (5)C16—C17—C18117.8 (4)
C7—C6—C3119.3 (5)C16—C17—H17A121.1
C5—C6—C3113.8 (4)C18—C17—H17A121.1
C7—C6—H6A93.4C17—C18—C13121.9 (4)
C5—C6—H6A93.4C17—C18—H18A119.0
C3—C6—H6A93.4C13—C18—H18A119.0
C10—N2—N3—C13178.6 (3)C10—C11—C12—C73.9 (6)
N1—C1—C2—C3−168 (3)C6—C7—C12—C11174.3 (5)
C1—C2—C3—C6165.2 (4)C8—C7—C12—C11−3.4 (6)
C4—C5—C6—C785.4 (7)N2—N3—C13—C141.4 (5)
C4—C5—C6—C3−82.7 (6)N2—N3—C13—C18−176.3 (3)
C2—C3—C6—C797.0 (6)N3—C13—C14—C15−179.6 (4)
C2—C3—C6—C5−94.1 (6)C18—C13—C14—C15−2.0 (6)
C5—C6—C7—C8−1.8 (9)C13—C14—C15—C16−0.8 (6)
C3—C6—C7—C8165.7 (4)C14—C15—C16—C173.1 (6)
C5—C6—C7—C12−179.3 (5)C14—C15—C16—N4−176.9 (4)
C3—C6—C7—C12−11.8 (8)O1—N4—C16—C15173.2 (4)
C6—C7—C8—C9−176.3 (5)O2—N4—C16—C15−5.0 (6)
C12—C7—C8—C91.4 (6)O1—N4—C16—C17−6.8 (6)
C7—C8—C9—C10−0.1 (7)O2—N4—C16—C17175.1 (4)
N3—N2—C10—C9−178.4 (3)C15—C16—C17—C18−2.3 (6)
N3—N2—C10—C11−0.3 (6)N4—C16—C17—C18177.6 (4)
C8—C9—C10—N2178.7 (4)C16—C17—C18—C13−0.7 (6)
C8—C9—C10—C110.4 (6)C14—C13—C18—C172.7 (6)
N2—C10—C11—C12179.6 (4)N3—C13—C18—C17−179.4 (4)
C9—C10—C11—C12−2.2 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2C···O1i0.972.463.343 (6)150
C9—H9A···Cg1ii0.932.923.713 (6)144
C15—H15A···Cg2ii0.932.903.690 (6)143

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2611).

References

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  • Bach, H., Anderle, K., Fuhrmann, Th. & Wendorff, J. H. (1996). J. Phys. Chem.100, 4135–4140.
  • Clark, R. J. H. & Hester, R. E. (1991). Advances in Materials Science Spectroscopy New York: John Wiley & Sons.
  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft. The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Taniike, K., Matsumoto, T., Sato, T., Ozaki, Y., Nakashima, K. & Iriyama, K. (1996). J. Phys. Chem.100, 15508–15516.
  • Zhao, X. Y., Hu, X., Yue, C. Y., Xia, X. L. & Gan, L. H. (2002). Thin Solid Films, 417, 95–100.

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