Acta Cryst. (2008). E64, o618 [ doi:10.1107/S1600536808004716 ]
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.
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).
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.
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./kp2153fig1thm.gif)
| Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./kp2153fig2thm.gif)
| 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. |
| C13H9N3O | F000 = 464 |
| Mr = 223.23 | Dx = 1.335 Mg m−3 |
| Monoclinic, Cc | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: C -2yc | Cell parameters from 4352 reflections |
| a = 6.5307 (13) Å | θ = 3.7–27.7º |
| b = 10.747 (2) Å | µ = 0.09 mm−1 |
| c = 15.851 (3) Å | T = 293 (2) K |
| β = 93.54 (3)º | BLOCK, yellow |
| V = 1110.4 (4) Å3 | 0.18 × 0.05 × 0.05 mm |
| Z = 4 |
| Rigaku Mercury2 diffractometer | 2532 independent reflections |
| Radiation source: fine-focus sealed tube | 1296 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.073 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5º |
| T = 293(2) K | θmin = 3.7º |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −13→13 |
| Tmin = 0.781, Tmax = 1 | l = −20→20 |
| 5599 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.053 | H-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 reflections | Δρmax = 0.17 e Å−3 |
| 154 parameters | Δρmin = −0.19 e Å−3 |
| 2 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods | Absolute structure: indeterminate |
| C13H9N3O | V = 1110.4 (4) Å3 |
| Mr = 223.23 | Z = 4 |
| Monoclinic, Cc | Mo Kα |
| a = 6.5307 (13) Å | µ = 0.09 mm−1 |
| b = 10.747 (2) Å | T = 293 (2) K |
| c = 15.851 (3) Å | 0.18 × 0.05 × 0.05 mm |
| β = 93.54 (3)º |
| Rigaku Mercury2 diffractometer | 2532 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1296 reflections with I > 2σ(I) |
| Tmin = 0.781, Tmax = 1 | Rint = 0.073 |
| 5599 measured reflections |
| R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.145 | Δρmax = 0.17 e Å−3 |
| S = 0.98 | Δρmin = −0.19 e Å−3 |
| 1278 reflections | Absolute structure: indeterminate |
| 154 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| N3 | 0.2824 (5) | 0.0455 (4) | 0.1896 (2) | 0.0497 (10) | |
| N2 | 0.1650 (5) | 0.1302 (4) | 0.1608 (2) | 0.0526 (11) | |
| C8 | 0.4581 (6) | 0.0892 (5) | 0.2376 (3) | 0.0447 (11) | |
| O1 | 0.9855 (5) | 0.1997 (4) | 0.3729 (2) | 0.0717 (11) | |
| H1A | 1.0618 | 0.1372 | 0.3848 | 0.108* | |
| 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) | |
| C12 | 0.7767 (7) | 0.0358 (5) | 0.3110 (3) | 0.0502 (11) | |
| H12A | 0.8709 | −0.0242 | 0.3303 | 0.060* | |
| 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) | |
| H6A | 0.0385 | −0.0988 | 0.1146 | 0.065* | |
| C2 | −0.3273 (7) | 0.1461 (5) | 0.0391 (3) | 0.0583 (14) | |
| H2B | −0.4188 | 0.2075 | 0.0197 | 0.070* | |
| C5 | −0.2315 (6) | −0.0695 (5) | 0.0497 (3) | 0.0565 (14) | |
| H5A | −0.2600 | −0.1526 | 0.0377 | 0.068* | |
| C9 | 0.4922 (6) | 0.2126 (4) | 0.2580 (3) | 0.0577 (13) | |
| H9A | 0.3959 | 0.2725 | 0.2407 | 0.069* | |
| C11 | 0.8129 (7) | 0.1589 (4) | 0.3289 (3) | 0.0513 (12) | |
| C13 | 0.6011 (7) | 0.0010 (5) | 0.2644 (3) | 0.0519 (13) | |
| H13A | 0.5788 | −0.0823 | 0.2511 | 0.062* | |
| C10 | 0.6682 (7) | 0.2471 (5) | 0.3040 (3) | 0.0622 (15) | |
| H10A | 0.6898 | 0.3302 | 0.3183 | 0.075* | |
| 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 | −0.1228 | 0.2613 | 0.0990 | 0.070* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N3 | 0.041 (2) | 0.055 (3) | 0.051 (2) | 0.000 (2) | −0.0098 (18) | 0.0033 (19) |
| N2 | 0.043 (2) | 0.054 (3) | 0.059 (3) | 0.002 (2) | −0.0175 (19) | 0.001 (2) |
| C8 | 0.031 (2) | 0.051 (3) | 0.051 (3) | 0.0005 (19) | −0.008 (2) | 0.000 (2) |
| O1 | 0.055 (2) | 0.071 (3) | 0.084 (3) | 0.0087 (18) | −0.0356 (19) | −0.014 (2) |
| C3 | 0.035 (2) | 0.070 (4) | 0.041 (2) | −0.005 (2) | −0.0080 (19) | 0.000 (2) |
| C7 | 0.042 (3) | 0.055 (3) | 0.039 (3) | −0.002 (2) | −0.010 (2) | 0.003 (2) |
| C12 | 0.039 (3) | 0.055 (3) | 0.055 (3) | 0.008 (2) | −0.012 (2) | 0.003 (2) |
| C4 | 0.046 (3) | 0.072 (4) | 0.052 (3) | −0.006 (3) | −0.006 (2) | −0.001 (2) |
| C6 | 0.045 (3) | 0.053 (3) | 0.063 (3) | 0.007 (2) | −0.017 (2) | −0.004 (3) |
| C2 | 0.054 (3) | 0.057 (3) | 0.061 (3) | 0.006 (2) | −0.019 (2) | 0.003 (2) |
| C5 | 0.053 (3) | 0.054 (3) | 0.060 (3) | 0.000 (2) | −0.009 (2) | −0.012 (2) |
| C9 | 0.045 (3) | 0.049 (3) | 0.076 (4) | 0.007 (2) | −0.023 (2) | 0.001 (3) |
| C11 | 0.046 (3) | 0.057 (3) | 0.049 (3) | −0.003 (2) | −0.010 (2) | −0.006 (2) |
| C13 | 0.045 (3) | 0.049 (3) | 0.061 (3) | 0.008 (2) | −0.007 (2) | −0.007 (2) |
| C10 | 0.055 (3) | 0.050 (3) | 0.078 (4) | 0.005 (2) | −0.021 (3) | −0.004 (3) |
| N1 | 0.048 (2) | 0.091 (3) | 0.072 (3) | −0.013 (2) | −0.017 (2) | −0.007 (2) |
| C1 | 0.051 (3) | 0.049 (3) | 0.071 (4) | −0.004 (2) | −0.021 (3) | 0.008 (2) |
| N3—N2 | 1.258 (4) | C12—H12A | 0.9300 |
| N3—C8 | 1.417 (5) | C4—N1 | 1.140 (6) |
| N2—C7 | 1.424 (5) | C6—C5 | 1.375 (7) |
| C8—C13 | 1.380 (6) | C6—H6A | 0.9300 |
| C8—C9 | 1.380 (6) | C2—C1 | 1.380 (6) |
| O1—C11 | 1.361 (5) | C2—H2B | 0.9300 |
| O1—H1A | 0.8501 | C5—H5A | 0.9300 |
| C3—C2 | 1.377 (7) | C9—C10 | 1.373 (6) |
| C3—C5 | 1.395 (7) | C9—H9A | 0.9300 |
| C3—C4 | 1.437 (6) | C11—C10 | 1.379 (7) |
| C7—C6 | 1.382 (6) | C13—H13A | 0.9300 |
| C7—C1 | 1.388 (6) | C10—H10A | 0.9300 |
| C12—C11 | 1.371 (7) | C1—H1B | 0.9300 |
| C12—C13 | 1.377 (7) | ||
| N2—N3—C8 | 114.2 (3) | C3—C2—H2B | 120.0 |
| N3—N2—C7 | 114.2 (3) | C1—C2—H2B | 120.0 |
| C13—C8—C9 | 119.4 (4) | C6—C5—C3 | 119.9 (4) |
| C13—C8—N3 | 116.6 (4) | C6—C5—H5A | 120.0 |
| C9—C8—N3 | 124.0 (4) | C3—C5—H5A | 120.0 |
| C11—O1—H1A | 108.4 | C10—C9—C8 | 120.1 (4) |
| C2—C3—C5 | 120.1 (4) | C10—C9—H9A | 119.9 |
| C2—C3—C4 | 119.9 (4) | C8—C9—H9A | 119.9 |
| C5—C3—C4 | 119.9 (5) | O1—C11—C12 | 122.9 (4) |
| C6—C7—C1 | 120.6 (4) | O1—C11—C10 | 117.2 (4) |
| C6—C7—N2 | 124.6 (4) | C12—C11—C10 | 119.9 (4) |
| C1—C7—N2 | 114.8 (4) | C12—C13—C8 | 120.3 (5) |
| C11—C12—C13 | 120.0 (4) | C12—C13—H13A | 119.8 |
| C11—C12—H12A | 120.0 | C8—C13—H13A | 119.8 |
| C13—C12—H12A | 120.0 | C9—C10—C11 | 120.2 (4) |
| N1—C4—C3 | 178.5 (6) | C9—C10—H10A | 119.9 |
| C5—C6—C7 | 119.7 (4) | C11—C10—H10A | 119.9 |
| C5—C6—H6A | 120.2 | C2—C1—C7 | 119.6 (5) |
| C7—C6—H6A | 120.2 | C2—C1—H1B | 120.2 |
| C3—C2—C1 | 120.0 (4) | C7—C1—H1B | 120.2 |
| C7—N2—N3—C8 | −179.2 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···N1i | 0.85 | 2.01 | 2.817 (5) | 159 |
| Symmetry codes: (i) x+2, −y, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···N1i | 0.85 | 2.01 | 2.817 (5) | 159 |
| Symmetry codes: (i) x+2, −y, z+1/2. |
This work was supported by a Start-up Grant from Southeast University to Dr Heng-Yun Ye. Dr Ye is not an author
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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.
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.