Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042157/rz6153sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042157/rz6153Isup2.hkl |
CCDC reference: 296644
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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).
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).
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).
C14H11ClN2O2 | F(000) = 568 |
Mr = 274.70 | Dx = 1.416 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 17972 reflections |
a = 8.4663 (15) Å | θ = 2.4–27.9° |
b = 11.236 (3) Å | µ = 0.30 mm−1 |
c = 13.955 (3) Å | T = 293 K |
β = 103.914 (14)° | Prism, red |
V = 1288.6 (5) Å3 | 0.40 × 0.35 × 0.29 mm |
Z = 4 |
STOE IPDS 2 diffractometer | 3078 independent reflections |
Radiation source: fine-focus sealed tube | 1780 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 6.67 pixels mm-1 | θmax = 28.0°, θmin = 2.4° |
ω scan rotation | h = −10→11 |
Absorption correction: integration X-RED32 (Stoe & Cie, 2002) | k = −14→14 |
Tmin = 0.887, Tmax = 0.952 | l = −18→18 |
21521 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-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 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C14H11ClN2O2 | V = 1288.6 (5) Å3 |
Mr = 274.70 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.4663 (15) Å | µ = 0.30 mm−1 |
b = 11.236 (3) Å | T = 293 K |
c = 13.955 (3) Å | 0.40 × 0.35 × 0.29 mm |
β = 103.914 (14)° |
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 = 0.952 | Rint = 0.059 |
21521 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.37 e Å−3 |
3078 reflections | Δρmin = −0.25 e Å−3 |
172 parameters |
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 | ||
C7 | 0.2963 (2) | 0.00359 (16) | 0.56885 (12) | 0.0584 (4) | |
C13 | 0.4364 (2) | 0.10318 (18) | 0.83267 (14) | 0.0640 (5) | |
C8 | 0.3809 (2) | 0.01002 (16) | 0.66559 (12) | 0.0567 (4) | |
H6 | 0.4619 | −0.0456 | 0.6899 | 0.068* | |
C9 | 0.3482 (2) | 0.09806 (15) | 0.72838 (12) | 0.0551 (4) | |
C2 | 0.4266 (2) | −0.28096 (17) | 0.41272 (14) | 0.0643 (5) | |
H11 | 0.4829 | −0.2780 | 0.4787 | 0.077* | |
C3 | 0.4595 (2) | −0.36781 (17) | 0.35033 (14) | 0.0619 (5) | |
C12 | 0.1771 (2) | 0.08755 (18) | 0.53261 (14) | 0.0678 (5) | |
H14 | 0.1197 | 0.0837 | 0.4669 | 0.081* | |
C6 | 0.2213 (3) | −0.20417 (18) | 0.27652 (15) | 0.0711 (5) | |
H15 | 0.1387 | −0.1499 | 0.2515 | 0.085* | |
C4 | 0.3776 (3) | −0.37212 (17) | 0.25323 (14) | 0.0687 (5) | |
H16 | 0.4029 | −0.4304 | 0.2120 | 0.082* | |
C11 | 0.1422 (3) | 0.17594 (18) | 0.59146 (16) | 0.0712 (5) | |
H17 | 0.0623 | 0.2319 | 0.5658 | 0.085* | |
C5 | 0.2582 (3) | −0.29034 (19) | 0.21673 (16) | 0.0762 (6) | |
H18 | 0.2020 | −0.2937 | 0.1508 | 0.091* | |
C14 | 0.5640 (3) | 0.0137 (2) | 0.87383 (16) | 0.0830 (6) | |
H19A | 0.6089 | 0.0300 | 0.9425 | 0.125* | |
H19B | 0.6486 | 0.0177 | 0.8389 | 0.125* | |
H19C | 0.5168 | −0.0645 | 0.8667 | 0.125* | |
C1 | 0.3053 (2) | −0.19717 (16) | 0.37325 (15) | 0.0634 (5) | |
C10 | 0.2274 (2) | 0.18180 (16) | 0.69064 (14) | 0.0630 (5) | |
N1 | 0.2614 (2) | −0.09958 (15) | 0.42815 (12) | 0.0691 (4) | |
N2 | 0.3424 (2) | −0.09615 (14) | 0.51426 (11) | 0.0647 (4) | |
O1 | 0.4041 (2) | 0.18066 (14) | 0.88686 (10) | 0.0838 (5) | |
O2 | 0.1871 (2) | 0.26841 (14) | 0.74578 (12) | 0.0866 (5) | |
H11A | 0.2424 | 0.2627 | 0.8025 | 0.130* | |
Cl1 | 0.60483 (8) | −0.47612 (6) | 0.39499 (4) | 0.0889 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C7 | 0.0699 (11) | 0.0572 (10) | 0.0489 (9) | −0.0075 (8) | 0.0156 (8) | −0.0041 (8) |
C13 | 0.0667 (12) | 0.0728 (12) | 0.0522 (9) | −0.0129 (9) | 0.0135 (9) | −0.0081 (9) |
C8 | 0.0649 (11) | 0.0529 (9) | 0.0530 (9) | −0.0036 (8) | 0.0159 (8) | −0.0007 (7) |
C9 | 0.0594 (10) | 0.0554 (10) | 0.0504 (9) | −0.0058 (8) | 0.0131 (8) | −0.0026 (7) |
C2 | 0.0692 (12) | 0.0696 (11) | 0.0536 (10) | −0.0111 (9) | 0.0139 (9) | −0.0078 (9) |
C3 | 0.0684 (11) | 0.0595 (10) | 0.0585 (10) | −0.0051 (8) | 0.0169 (9) | −0.0058 (8) |
C12 | 0.0748 (12) | 0.0749 (12) | 0.0503 (9) | −0.0062 (10) | 0.0085 (9) | −0.0019 (9) |
C6 | 0.0801 (14) | 0.0660 (12) | 0.0620 (11) | −0.0011 (10) | 0.0070 (10) | 0.0016 (9) |
C4 | 0.0917 (14) | 0.0579 (10) | 0.0576 (10) | −0.0079 (10) | 0.0199 (10) | −0.0080 (9) |
C11 | 0.0710 (12) | 0.0704 (12) | 0.0665 (12) | 0.0076 (10) | 0.0058 (10) | 0.0019 (10) |
C5 | 0.0939 (15) | 0.0696 (12) | 0.0593 (11) | −0.0058 (11) | 0.0071 (11) | −0.0015 (10) |
C14 | 0.0852 (15) | 0.0985 (16) | 0.0590 (11) | 0.0070 (12) | 0.0048 (10) | 0.0014 (11) |
C1 | 0.0716 (12) | 0.0530 (10) | 0.0702 (12) | −0.0071 (9) | 0.0259 (10) | −0.0080 (8) |
C10 | 0.0668 (12) | 0.0604 (11) | 0.0625 (11) | −0.0003 (9) | 0.0168 (9) | −0.0090 (9) |
N1 | 0.0741 (10) | 0.0707 (10) | 0.0601 (9) | −0.0028 (8) | 0.0113 (8) | 0.0001 (8) |
N2 | 0.0722 (10) | 0.0713 (10) | 0.0493 (8) | −0.0081 (8) | 0.0123 (7) | −0.0021 (7) |
O1 | 0.0938 (11) | 0.0935 (10) | 0.0611 (8) | −0.0034 (8) | 0.0124 (8) | −0.0256 (8) |
O2 | 0.0938 (10) | 0.0792 (9) | 0.0823 (10) | 0.0191 (8) | 0.0123 (8) | −0.0234 (8) |
Cl1 | 0.0918 (4) | 0.0914 (4) | 0.0800 (4) | 0.0227 (3) | 0.0140 (3) | −0.0031 (3) |
C7—C8 | 1.370 (2) | C6—C5 | 1.363 (3) |
C7—C12 | 1.385 (3) | C6—C1 | 1.368 (3) |
C7—N2 | 1.460 (2) | C6—H15 | 0.9300 |
C13—O1 | 1.226 (2) | C4—C5 | 1.370 (3) |
C13—C9 | 1.468 (2) | C4—H16 | 0.9300 |
C13—C14 | 1.486 (3) | C11—C10 | 1.400 (3) |
C8—C9 | 1.393 (2) | C11—H17 | 0.9300 |
C8—H6 | 0.9300 | C5—H18 | 0.9300 |
C9—C10 | 1.396 (3) | C14—H19A | 0.9600 |
C2—C3 | 1.380 (3) | C14—H19B | 0.9600 |
C2—C1 | 1.404 (3) | C14—H19C | 0.9600 |
C2—H11 | 0.9300 | C1—N1 | 1.437 (2) |
C3—C4 | 1.366 (3) | C10—O2 | 1.335 (2) |
C3—Cl1 | 1.736 (2) | N1—N2 | 1.233 (2) |
C12—C11 | 1.366 (3) | O2—H11A | 0.8200 |
C12—H14 | 0.9300 | ||
C8—C7—C12 | 119.11 (17) | C3—C4—C5 | 119.86 (19) |
C8—C7—N2 | 114.37 (16) | C3—C4—H16 | 120.1 |
C12—C7—N2 | 126.51 (16) | C5—C4—H16 | 120.1 |
O1—C13—C9 | 120.21 (19) | C12—C11—C10 | 119.62 (19) |
O1—C13—C14 | 119.41 (18) | C12—C11—H17 | 120.2 |
C9—C13—C14 | 120.38 (18) | C10—C11—H17 | 120.2 |
C7—C8—C9 | 121.45 (17) | C6—C5—C4 | 120.41 (19) |
C7—C8—H6 | 119.3 | C6—C5—H18 | 119.8 |
C9—C8—H6 | 119.3 | C4—C5—H18 | 119.8 |
C8—C9—C10 | 118.65 (16) | C13—C14—H19A | 109.5 |
C8—C9—C13 | 121.39 (17) | C13—C14—H19B | 109.5 |
C10—C9—C13 | 119.96 (17) | H19A—C14—H19B | 109.5 |
C3—C2—C1 | 117.77 (18) | C13—C14—H19C | 109.5 |
C3—C2—H11 | 121.1 | H19A—C14—H19C | 109.5 |
C1—C2—H11 | 121.1 | H19B—C14—H19C | 109.5 |
C4—C3—C2 | 121.30 (19) | C6—C1—C2 | 120.40 (17) |
C4—C3—Cl1 | 118.55 (15) | C6—C1—N1 | 115.47 (18) |
C2—C3—Cl1 | 120.14 (15) | C2—C1—N1 | 124.12 (17) |
C11—C12—C7 | 121.31 (18) | O2—C10—C9 | 122.65 (17) |
C11—C12—H14 | 119.3 | O2—C10—C11 | 117.49 (18) |
C7—C12—H14 | 119.3 | C9—C10—C11 | 119.85 (17) |
C5—C6—C1 | 120.2 (2) | N2—N1—C1 | 112.89 (17) |
C5—C6—H15 | 119.9 | N1—N2—C7 | 112.13 (16) |
C1—C6—H15 | 119.9 | C10—O2—H11A | 109.5 |
C12—C7—C8—C9 | 0.9 (3) | C3—C4—C5—C6 | 0.5 (3) |
N2—C7—C8—C9 | −178.20 (15) | C5—C6—C1—C2 | −2.1 (3) |
C7—C8—C9—C10 | −0.7 (3) | C5—C6—C1—N1 | 177.20 (18) |
C7—C8—C9—C13 | 178.56 (16) | C3—C2—C1—C6 | 1.3 (3) |
O1—C13—C9—C8 | −179.07 (17) | C3—C2—C1—N1 | −177.90 (17) |
C14—C13—C9—C8 | 0.1 (3) | C8—C9—C10—O2 | 179.30 (17) |
O1—C13—C9—C10 | 0.2 (3) | C13—C9—C10—O2 | 0.0 (3) |
C14—C13—C9—C10 | 179.34 (18) | C8—C9—C10—C11 | 0.0 (3) |
C1—C2—C3—C4 | 0.3 (3) | C13—C9—C10—C11 | −179.29 (18) |
C1—C2—C3—Cl1 | −178.58 (14) | C12—C11—C10—O2 | −178.78 (19) |
C8—C7—C12—C11 | −0.3 (3) | C12—C11—C10—C9 | 0.6 (3) |
N2—C7—C12—C11 | 178.64 (18) | C6—C1—N1—N2 | −178.84 (17) |
C2—C3—C4—C5 | −1.2 (3) | C2—C1—N1—N2 | 0.4 (3) |
Cl1—C3—C4—C5 | 177.70 (16) | C1—N1—N2—C7 | 179.93 (14) |
C7—C12—C11—C10 | −0.4 (3) | C8—C7—N2—N1 | 178.86 (16) |
C1—C6—C5—C4 | 1.2 (3) | C12—C7—N2—N1 | −0.1 (3) |
Experimental details
Crystal data | |
Chemical formula | C14H11ClN2O2 |
Mr | 274.70 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.4663 (15), 11.236 (3), 13.955 (3) |
β (°) | 103.914 (14) |
V (Å3) | 1288.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.40 × 0.35 × 0.29 |
Data collection | |
Diffractometer | STOE IPDS 2 diffractometer |
Absorption correction | Integration X-RED32 (Stoe & Cie, 2002) |
Tmin, Tmax | 0.887, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21521, 3078, 1780 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.134, 0.97 |
No. of reflections | 3078 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
C7—N2 | 1.460 (2) | C1—N1 | 1.437 (2) |
C13—O1 | 1.226 (2) | C10—O2 | 1.335 (2) |
C3—Cl1 | 1.736 (2) | N1—N2 | 1.233 (2) |
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.