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The mol­ecule of the title compound, C13H10ClN2O2, is essentially planar and displays a trans configuration with respect to the central N=N double bond. The dihedral angle between the two aromatic rings is 0.73 (16)°. There is a strong intra­molecular O—H...O hydrogen-bonding inter­action which stabilizes the mol­ecular structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042157/rz6153sup1.cif
Contains datablocks samc13, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042157/rz6153Isup2.hkl
Contains datablock I

CCDC reference: 296644

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.043
  • wR factor = 0.134
  • Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for N1 - C1 .. 12.68 su PLAT230_ALERT_2_B Hirshfeld Test Diff for N2 - C7 .. 9.05 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C1 - C6 .. 8.40 su
Alert level C PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - N2 .. 6.13 su PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C14
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The extensive application of azo dyes in industry and analytical determinations has attracted attention for decades. Azo dyes incorporating `push–pull' donor–acceptor aryl rings are of great commercial importance for the dyeing of textiles (Zollinger, 1994).

The molecular structure of (I) is shown in Fig. 1 with the atom-numbering scheme. Selected bond lengths and angles are listed in Table 1. In the azo group, the N1—C1 and N2—C7 bond lengths indicate significant single-bond character, whereas the N1=N2 bond length is indicative of significant double-bond character.

The molecule is essentially planar, the dihedral angle formed by the aromatic rings being 179.27 (16)°. A strong intramolecular O—H···H hydrogen bond (Table 2) stabilizes the molecular structure.

Experimental top

A mixture of 3-chloroaniline (1 g, 7.8 mmol), water (20 ml) and concentrated hydrochloric acid (1.97 ml, 23.4 mmol) was stirred until a clear solution was obtained. This solution was cooled to 273–278 K and a nitrite solution (0.75 g, 7.8 mmol) in water was added dropwise while the temperature was maintained below 278 K. The resulting mixture was stirred for 30 min in an ice bath. 2-Hydroxyacetophenone (1.067 g, 7.8 mmol) solution (pH 9) was gradually added to a cooled solution of 3-chlorobenzenediazonium chloride, prepared as described above, and the resulting mixture was stirred at 273–278 K for 60 min in an ice bath. Crystals suitable for X-ray analysis were obtained after 1 d by slow evaporation of an ethanol solution (yield 79%, m.p. 385–387 K).

Refinement top

All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93–0.96 Å, O—H = 0.82 Å, and with Uiso(H) = 1.2–1.5 Ueq(parent atom).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. An ORTEP view of the title compound, with the atom-numbering scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram of (I), approximately viewed along the [110] direction. Intramolecular O—H···O hydrogen bonds are shown as dotted lines.
(E)-2-Acetyl-4-[(3-chlorophenyl)diazenyl]phenol top
Crystal data top
C14H11ClN2O2F(000) = 568
Mr = 274.70Dx = 1.416 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 17972 reflections
a = 8.4663 (15) Åθ = 2.4–27.9°
b = 11.236 (3) ŵ = 0.30 mm1
c = 13.955 (3) ÅT = 293 K
β = 103.914 (14)°Prism, red
V = 1288.6 (5) Å30.40 × 0.35 × 0.29 mm
Z = 4
Data collection top
STOE IPDS 2
diffractometer
3078 independent reflections
Radiation source: fine-focus sealed tube1780 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 6.67 pixels mm-1θmax = 28.0°, θmin = 2.4°
ω scan rotationh = 1011
Absorption correction: integration
X-RED32 (Stoe & Cie, 2002)
k = 1414
Tmin = 0.887, Tmax = 0.952l = 1818
21521 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0783P)2]
where P = (Fo2 + 2Fc2)/3
3078 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C14H11ClN2O2V = 1288.6 (5) Å3
Mr = 274.70Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.4663 (15) ŵ = 0.30 mm1
b = 11.236 (3) ÅT = 293 K
c = 13.955 (3) Å0.40 × 0.35 × 0.29 mm
β = 103.914 (14)°
Data collection top
STOE IPDS 2
diffractometer
3078 independent reflections
Absorption correction: integration
X-RED32 (Stoe & Cie, 2002)
1780 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.952Rint = 0.059
21521 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 0.97Δρmax = 0.37 e Å3
3078 reflectionsΔρmin = 0.25 e Å3
172 parameters
Special details top

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) top
xyzUiso*/Ueq
C70.2963 (2)0.00359 (16)0.56885 (12)0.0584 (4)
C130.4364 (2)0.10318 (18)0.83267 (14)0.0640 (5)
C80.3809 (2)0.01002 (16)0.66559 (12)0.0567 (4)
H60.46190.04560.68990.068*
C90.3482 (2)0.09806 (15)0.72838 (12)0.0551 (4)
C20.4266 (2)0.28096 (17)0.41272 (14)0.0643 (5)
H110.48290.27800.47870.077*
C30.4595 (2)0.36781 (17)0.35033 (14)0.0619 (5)
C120.1771 (2)0.08755 (18)0.53261 (14)0.0678 (5)
H140.11970.08370.46690.081*
C60.2213 (3)0.20417 (18)0.27652 (15)0.0711 (5)
H150.13870.14990.25150.085*
C40.3776 (3)0.37212 (17)0.25323 (14)0.0687 (5)
H160.40290.43040.21200.082*
C110.1422 (3)0.17594 (18)0.59146 (16)0.0712 (5)
H170.06230.23190.56580.085*
C50.2582 (3)0.29034 (19)0.21673 (16)0.0762 (6)
H180.20200.29370.15080.091*
C140.5640 (3)0.0137 (2)0.87383 (16)0.0830 (6)
H19A0.60890.03000.94250.125*
H19B0.64860.01770.83890.125*
H19C0.51680.06450.86670.125*
C10.3053 (2)0.19717 (16)0.37325 (15)0.0634 (5)
C100.2274 (2)0.18180 (16)0.69064 (14)0.0630 (5)
N10.2614 (2)0.09958 (15)0.42815 (12)0.0691 (4)
N20.3424 (2)0.09615 (14)0.51426 (11)0.0647 (4)
O10.4041 (2)0.18066 (14)0.88686 (10)0.0838 (5)
O20.1871 (2)0.26841 (14)0.74578 (12)0.0866 (5)
H11A0.24240.26270.80250.130*
Cl10.60483 (8)0.47612 (6)0.39499 (4)0.0889 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C70.0699 (11)0.0572 (10)0.0489 (9)0.0075 (8)0.0156 (8)0.0041 (8)
C130.0667 (12)0.0728 (12)0.0522 (9)0.0129 (9)0.0135 (9)0.0081 (9)
C80.0649 (11)0.0529 (9)0.0530 (9)0.0036 (8)0.0159 (8)0.0007 (7)
C90.0594 (10)0.0554 (10)0.0504 (9)0.0058 (8)0.0131 (8)0.0026 (7)
C20.0692 (12)0.0696 (11)0.0536 (10)0.0111 (9)0.0139 (9)0.0078 (9)
C30.0684 (11)0.0595 (10)0.0585 (10)0.0051 (8)0.0169 (9)0.0058 (8)
C120.0748 (12)0.0749 (12)0.0503 (9)0.0062 (10)0.0085 (9)0.0019 (9)
C60.0801 (14)0.0660 (12)0.0620 (11)0.0011 (10)0.0070 (10)0.0016 (9)
C40.0917 (14)0.0579 (10)0.0576 (10)0.0079 (10)0.0199 (10)0.0080 (9)
C110.0710 (12)0.0704 (12)0.0665 (12)0.0076 (10)0.0058 (10)0.0019 (10)
C50.0939 (15)0.0696 (12)0.0593 (11)0.0058 (11)0.0071 (11)0.0015 (10)
C140.0852 (15)0.0985 (16)0.0590 (11)0.0070 (12)0.0048 (10)0.0014 (11)
C10.0716 (12)0.0530 (10)0.0702 (12)0.0071 (9)0.0259 (10)0.0080 (8)
C100.0668 (12)0.0604 (11)0.0625 (11)0.0003 (9)0.0168 (9)0.0090 (9)
N10.0741 (10)0.0707 (10)0.0601 (9)0.0028 (8)0.0113 (8)0.0001 (8)
N20.0722 (10)0.0713 (10)0.0493 (8)0.0081 (8)0.0123 (7)0.0021 (7)
O10.0938 (11)0.0935 (10)0.0611 (8)0.0034 (8)0.0124 (8)0.0256 (8)
O20.0938 (10)0.0792 (9)0.0823 (10)0.0191 (8)0.0123 (8)0.0234 (8)
Cl10.0918 (4)0.0914 (4)0.0800 (4)0.0227 (3)0.0140 (3)0.0031 (3)
Geometric parameters (Å, º) top
C7—C81.370 (2)C6—C51.363 (3)
C7—C121.385 (3)C6—C11.368 (3)
C7—N21.460 (2)C6—H150.9300
C13—O11.226 (2)C4—C51.370 (3)
C13—C91.468 (2)C4—H160.9300
C13—C141.486 (3)C11—C101.400 (3)
C8—C91.393 (2)C11—H170.9300
C8—H60.9300C5—H180.9300
C9—C101.396 (3)C14—H19A0.9600
C2—C31.380 (3)C14—H19B0.9600
C2—C11.404 (3)C14—H19C0.9600
C2—H110.9300C1—N11.437 (2)
C3—C41.366 (3)C10—O21.335 (2)
C3—Cl11.736 (2)N1—N21.233 (2)
C12—C111.366 (3)O2—H11A0.8200
C12—H140.9300
C8—C7—C12119.11 (17)C3—C4—C5119.86 (19)
C8—C7—N2114.37 (16)C3—C4—H16120.1
C12—C7—N2126.51 (16)C5—C4—H16120.1
O1—C13—C9120.21 (19)C12—C11—C10119.62 (19)
O1—C13—C14119.41 (18)C12—C11—H17120.2
C9—C13—C14120.38 (18)C10—C11—H17120.2
C7—C8—C9121.45 (17)C6—C5—C4120.41 (19)
C7—C8—H6119.3C6—C5—H18119.8
C9—C8—H6119.3C4—C5—H18119.8
C8—C9—C10118.65 (16)C13—C14—H19A109.5
C8—C9—C13121.39 (17)C13—C14—H19B109.5
C10—C9—C13119.96 (17)H19A—C14—H19B109.5
C3—C2—C1117.77 (18)C13—C14—H19C109.5
C3—C2—H11121.1H19A—C14—H19C109.5
C1—C2—H11121.1H19B—C14—H19C109.5
C4—C3—C2121.30 (19)C6—C1—C2120.40 (17)
C4—C3—Cl1118.55 (15)C6—C1—N1115.47 (18)
C2—C3—Cl1120.14 (15)C2—C1—N1124.12 (17)
C11—C12—C7121.31 (18)O2—C10—C9122.65 (17)
C11—C12—H14119.3O2—C10—C11117.49 (18)
C7—C12—H14119.3C9—C10—C11119.85 (17)
C5—C6—C1120.2 (2)N2—N1—C1112.89 (17)
C5—C6—H15119.9N1—N2—C7112.13 (16)
C1—C6—H15119.9C10—O2—H11A109.5
C12—C7—C8—C90.9 (3)C3—C4—C5—C60.5 (3)
N2—C7—C8—C9178.20 (15)C5—C6—C1—C22.1 (3)
C7—C8—C9—C100.7 (3)C5—C6—C1—N1177.20 (18)
C7—C8—C9—C13178.56 (16)C3—C2—C1—C61.3 (3)
O1—C13—C9—C8179.07 (17)C3—C2—C1—N1177.90 (17)
C14—C13—C9—C80.1 (3)C8—C9—C10—O2179.30 (17)
O1—C13—C9—C100.2 (3)C13—C9—C10—O20.0 (3)
C14—C13—C9—C10179.34 (18)C8—C9—C10—C110.0 (3)
C1—C2—C3—C40.3 (3)C13—C9—C10—C11179.29 (18)
C1—C2—C3—Cl1178.58 (14)C12—C11—C10—O2178.78 (19)
C8—C7—C12—C110.3 (3)C12—C11—C10—C90.6 (3)
N2—C7—C12—C11178.64 (18)C6—C1—N1—N2178.84 (17)
C2—C3—C4—C51.2 (3)C2—C1—N1—N20.4 (3)
Cl1—C3—C4—C5177.70 (16)C1—N1—N2—C7179.93 (14)
C7—C12—C11—C100.4 (3)C8—C7—N2—N1178.86 (16)
C1—C6—C5—C41.2 (3)C12—C7—N2—N10.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H11A···O10.821.832.547 (2)146

Experimental details

Crystal data
Chemical formulaC14H11ClN2O2
Mr274.70
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)8.4663 (15), 11.236 (3), 13.955 (3)
β (°) 103.914 (14)
V3)1288.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.40 × 0.35 × 0.29
Data collection
DiffractometerSTOE IPDS 2
diffractometer
Absorption correctionIntegration
X-RED32 (Stoe & Cie, 2002)
Tmin, Tmax0.887, 0.952
No. of measured, independent and
observed [I > 2σ(I)] reflections
21521, 3078, 1780
Rint0.059
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.134, 0.97
No. of reflections3078
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.25

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
C7—N21.460 (2)C1—N11.437 (2)
C13—O11.226 (2)C10—O21.335 (2)
C3—Cl11.736 (2)N1—N21.233 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H11A···O10.821.832.547 (2)145.9
 

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