PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o618.
Published online 2008 February 22. doi:  10.1107/S1600536808004716
PMCID: PMC2960800

4-(4-Hydroxy­phenyl­diazen­yl)­benzonitrile

Abstract

The molecule of the title compound, C13H9N3O, is achiral but forms a chiral arrangement in the crystal structure. The mol­ecule adopts an E configuration with respect to the N=N bond and is almost planar, with an r.m.s. deviation of 0.0439 Å from the plane through all atoms in the mol­ecule. The dihedral angle between the two benzene rings is 2.2 (2)°. In the crystal structure, inter­molecular O—H(...)N hydrogen bonding generates a chain.

Related literature

For the preparation of tetra­zole derivatives from nitrile compounds, see: Dunica et al. (1991 [triangle]); Wittenberger & Donner (1993 [triangle]). For the general chemistry of tetra­zole compounds, see: Xiong et al. (2002 [triangle]). For a similar structure, see: Harada et al. (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o618-scheme1.jpg

Experimental

Crystal data

  • C13H9N3O
  • M r = 223.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o618-efi1.jpg
  • a = 6.5307 (13) Å
  • b = 10.747 (2) Å
  • c = 15.851 (3) Å
  • β = 93.54 (3)°
  • V = 1110.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 (2) K
  • 0.18 × 0.05 × 0.05 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.781, T max = 1 (expected range = 0.778–0.996)
  • 5599 measured reflections
  • 2532 independent reflections
  • 1296 reflections with I > 2σ(I)
  • R int = 0.073

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.145
  • S = 0.97
  • 1278 reflections
  • 154 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.19 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004716/kp2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004716/kp2153Isup2.hkl

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

Acknowledgments

This work was supported by a Start-up Grant from Southeast University to Dr Chao Zhi Zhang.

supplementary crystallographic information

Comment

Nitrile compounds are the precursor of tetrazole derivatives (Dunica, et al., 1991; Wittenberger, et al., 1993) and can be used for the design of noncentrosymmetric bulk materials (Xiong, et al.(2002)). We report here the crystal structure of the title compound, 4-(4-hydroxyphenylazo)benzonitrile, (I) (Fig. 1).

In I, the N=N double bond [1.257 (4) Å] is in the range found in other similar azo complexes with a trans-configuration (Harada, et al., 1997). The torsion angle C7 - N2 - N3 - C8 is -179.30 (0.32)°. The dihedral angle between the two benzene rings is 2.18 (1/5) °. The crystal structure involves O—H···N hydrogen bond resulting in the formation of a chain.

Experimental

A solution of 4-cyanoaniline (0.71 g, 6 mmol) in a solution of hydrochloric acid (6 ml, 4M) was added to a solution of sodium nitrite (0.42 g, 6.1 mmol) in 2 ml water, and the mixture was stirred for 4 h under N2 atmosphere at 273–278 K. Then urea (0.01 g, 0.2 mmol) was added to decompose excessive nitrous acid, and the mixture was further stirred for 30 min. The solution of the diazonium salt was added to a aqueous phenol (0.62 g, 6.6 mmol), sodium carbonate (3 g), baking soda (0.2 g) and ice (15 g) at 273–278 K. The mixture was stirred for 7 h. After the reaction solution was neutralized with a solution of hydrochoric acid (13.6 ml, 3 M), the mixture was filtrated. A yellow block-like crystals (1.27 g, 5.7 mmol, 95%), which is suitable for X-ray analysis, were obtained by recrystallization from ethyl acetate (18 ml).

Refinement

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C),orUiso(H) = 1.2Ueq(O). In the absence of significant anomalous scattering effects the Friedel pairs were merged.

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound viewed along the a axis. Hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

Crystal data

C13H9N3OF000 = 464
Mr = 223.23Dx = 1.335 Mg m3
Monoclinic, CcMo Kα radiation λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 4352 reflections
a = 6.5307 (13) Åθ = 3.7–27.7º
b = 10.747 (2) ŵ = 0.09 mm1
c = 15.851 (3) ÅT = 293 (2) K
β = 93.54 (3)ºBLOCK, yellow
V = 1110.4 (4) Å30.18 × 0.05 × 0.05 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer2532 independent reflections
Radiation source: fine-focus sealed tube1296 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.073
Detector resolution: 13.6612 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.7º
ω scansh = −8→8
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −13→13
Tmin = 0.781, Tmax = 1l = −20→20
5599 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.145  w = 1/[σ2(Fo2) + (0.0762P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
1278 reflectionsΔρmax = 0.17 e Å3
154 parametersΔρmin = −0.19 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: indeterminate

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
N30.2824 (5)0.0455 (4)0.1896 (2)0.0497 (10)
N20.1650 (5)0.1302 (4)0.1608 (2)0.0526 (11)
C80.4581 (6)0.0892 (5)0.2376 (3)0.0447 (11)
O10.9855 (5)0.1997 (4)0.3729 (2)0.0717 (11)
H1A1.06180.13720.38480.108*
C3−0.3689 (6)0.0230 (5)0.0211 (3)0.0493 (12)
C7−0.0130 (6)0.0862 (4)0.1136 (3)0.0457 (11)
C120.7767 (7)0.0358 (5)0.3110 (3)0.0502 (11)
H12A0.8709−0.02420.33030.060*
C4−0.5570 (7)−0.0106 (5)−0.0251 (3)0.0572 (13)
C6−0.0538 (7)−0.0375 (5)0.0957 (3)0.0543 (13)
H6A0.0385−0.09880.11460.065*
C2−0.3273 (7)0.1461 (5)0.0391 (3)0.0583 (14)
H2B−0.41880.20750.01970.070*
C5−0.2315 (6)−0.0695 (5)0.0497 (3)0.0565 (14)
H5A−0.2600−0.15260.03770.068*
C90.4922 (6)0.2126 (4)0.2580 (3)0.0577 (13)
H9A0.39590.27250.24070.069*
C110.8129 (7)0.1589 (4)0.3289 (3)0.0513 (12)
C130.6011 (7)0.0010 (5)0.2644 (3)0.0519 (13)
H13A0.5788−0.08230.25110.062*
C100.6682 (7)0.2471 (5)0.3040 (3)0.0622 (15)
H10A0.68980.33020.31830.075*
N1−0.7085 (7)−0.0361 (5)−0.0604 (3)0.0712 (12)
C1−0.1502 (7)0.1783 (5)0.0860 (3)0.0580 (14)
H1B−0.12280.26130.09900.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N30.041 (2)0.055 (3)0.051 (2)0.000 (2)−0.0098 (18)0.0033 (19)
N20.043 (2)0.054 (3)0.059 (3)0.002 (2)−0.0175 (19)0.001 (2)
C80.031 (2)0.051 (3)0.051 (3)0.0005 (19)−0.008 (2)0.000 (2)
O10.055 (2)0.071 (3)0.084 (3)0.0087 (18)−0.0356 (19)−0.014 (2)
C30.035 (2)0.070 (4)0.041 (2)−0.005 (2)−0.0080 (19)0.000 (2)
C70.042 (3)0.055 (3)0.039 (3)−0.002 (2)−0.010 (2)0.003 (2)
C120.039 (3)0.055 (3)0.055 (3)0.008 (2)−0.012 (2)0.003 (2)
C40.046 (3)0.072 (4)0.052 (3)−0.006 (3)−0.006 (2)−0.001 (2)
C60.045 (3)0.053 (3)0.063 (3)0.007 (2)−0.017 (2)−0.004 (3)
C20.054 (3)0.057 (3)0.061 (3)0.006 (2)−0.019 (2)0.003 (2)
C50.053 (3)0.054 (3)0.060 (3)0.000 (2)−0.009 (2)−0.012 (2)
C90.045 (3)0.049 (3)0.076 (4)0.007 (2)−0.023 (2)0.001 (3)
C110.046 (3)0.057 (3)0.049 (3)−0.003 (2)−0.010 (2)−0.006 (2)
C130.045 (3)0.049 (3)0.061 (3)0.008 (2)−0.007 (2)−0.007 (2)
C100.055 (3)0.050 (3)0.078 (4)0.005 (2)−0.021 (3)−0.004 (3)
N10.048 (2)0.091 (3)0.072 (3)−0.013 (2)−0.017 (2)−0.007 (2)
C10.051 (3)0.049 (3)0.071 (4)−0.004 (2)−0.021 (3)0.008 (2)

Geometric parameters (Å, °)

N3—N21.258 (4)C12—H12A0.9300
N3—C81.417 (5)C4—N11.140 (6)
N2—C71.424 (5)C6—C51.375 (7)
C8—C131.380 (6)C6—H6A0.9300
C8—C91.380 (6)C2—C11.380 (6)
O1—C111.361 (5)C2—H2B0.9300
O1—H1A0.8501C5—H5A0.9300
C3—C21.377 (7)C9—C101.373 (6)
C3—C51.395 (7)C9—H9A0.9300
C3—C41.437 (6)C11—C101.379 (7)
C7—C61.382 (6)C13—H13A0.9300
C7—C11.388 (6)C10—H10A0.9300
C12—C111.371 (7)C1—H1B0.9300
C12—C131.377 (7)
N2—N3—C8114.2 (3)C3—C2—H2B120.0
N3—N2—C7114.2 (3)C1—C2—H2B120.0
C13—C8—C9119.4 (4)C6—C5—C3119.9 (4)
C13—C8—N3116.6 (4)C6—C5—H5A120.0
C9—C8—N3124.0 (4)C3—C5—H5A120.0
C11—O1—H1A108.4C10—C9—C8120.1 (4)
C2—C3—C5120.1 (4)C10—C9—H9A119.9
C2—C3—C4119.9 (4)C8—C9—H9A119.9
C5—C3—C4119.9 (5)O1—C11—C12122.9 (4)
C6—C7—C1120.6 (4)O1—C11—C10117.2 (4)
C6—C7—N2124.6 (4)C12—C11—C10119.9 (4)
C1—C7—N2114.8 (4)C12—C13—C8120.3 (5)
C11—C12—C13120.0 (4)C12—C13—H13A119.8
C11—C12—H12A120.0C8—C13—H13A119.8
C13—C12—H12A120.0C9—C10—C11120.2 (4)
N1—C4—C3178.5 (6)C9—C10—H10A119.9
C5—C6—C7119.7 (4)C11—C10—H10A119.9
C5—C6—H6A120.2C2—C1—C7119.6 (5)
C7—C6—H6A120.2C2—C1—H1B120.2
C3—C2—C1120.0 (4)C7—C1—H1B120.2
C7—N2—N3—C8−179.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···N1i0.852.012.817 (5)159

Symmetry codes: (i) x+2, −y, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2153).

References

  • Dunica, J. V., Pierce, M. E. & Santella, J. B. III (1991). J. Org. Chem., 56, 2395-2400.
  • Harada, J., Ogawa, K. & Tomoda, S. (1997). Acta Cryst. B53, 662–672.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wittenberger, S. J. & Donner, B. G. (1993). J. Org. Chem., 58, 4139-4141.
  • Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed.41, 3800–3803. [PubMed]

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