organic compounds
N′-[(E)-1-(5-Bromo-2-hydroxyphenyl)ethylidene]benzohydrazide
aCollege of Environmental and Chemical Engineering, Xi'an Polytechnic University, 710048 Xi'an, Shaanxi, People's Republic of China, and bDepartment of Materials Science and Chemical Engineering, Sichuan University of Science and Engineering , 643000 Zigong, Sichuan, People's Republic of China
*Correspondence e-mail: jichangyou789456@126.com
The C=N double bond in the title compound, C15H13BrN2O2, is trans E configured and the dihedral angle between the aromatic ring planes is 22.3 (1)°. The is stabilized by intramolecular O—H⋯O and intermolecular N—H⋯O hydrogen bonds.
Related literature
For aroylhydrazones and their biological activity, see: Singh et al. (1982); Salem (1998); Carcelli et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536808039755/bt2814sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808039755/bt2814Isup2.hkl
Benzoylhydrazine (0.02 mol, 2.72 g) was dissolved in anhydrous ethanol (50 ml), and 1-(5-bromo-2-hydroxyphenyl)ethanone (0.02 mol, 4.30 g) was added. The reaction mixture was refluxed for 6 h with stirring, then the resulting precipitate was collected by filtration, washed several times with ethanol and dried in vacuo (yield 85%). The compound (2.0 mmol, 0.67 g) was dissolved in dimethylformamide (30 ml) and kept at room temperature for 30 d to obtain yellow single crystals suitable for X-ray diffraction.
All H atoms were positioned geometrically and treated as riding on their parent atoms,with C—H(methyl) = 0.96 Å, C—H(aromatic) = 0.93 Å, O—H = 0.82 Å, and N—H = 0.86 Å and with Uiso(H) =1.5Ueq(Cmethyl,O) and 1.2Ueq(Caromatic,N).
Data collection: SMART (Siemens, 1996); cell
SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).C15H13BrN2O2 | F(000) = 672 |
Mr = 333.18 | Dx = 1.383 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1189 reflections |
a = 7.3761 (15) Å | θ = 2.9–20.7° |
b = 28.270 (6) Å | µ = 2.57 mm−1 |
c = 8.6089 (13) Å | T = 298 K |
β = 116.928 (12)° | Block, yellow |
V = 1600.5 (5) Å3 | 0.12 × 0.08 × 0.06 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2830 independent reflections |
Radiation source: fine-focus sealed tube | 1490 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ϕ and ω scans | θmax = 25.1°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.748, Tmax = 0.861 | k = −33→33 |
8028 measured reflections | l = −7→10 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.089P)2 + 0.7896P] where P = (Fo2 + 2Fc2)/3 |
2830 reflections | (Δ/σ)max = 0.002 |
183 parameters | Δρmax = 0.87 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C15H13BrN2O2 | V = 1600.5 (5) Å3 |
Mr = 333.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3761 (15) Å | µ = 2.57 mm−1 |
b = 28.270 (6) Å | T = 298 K |
c = 8.6089 (13) Å | 0.12 × 0.08 × 0.06 mm |
β = 116.928 (12)° |
Siemens SMART CCD area-detector diffractometer | 2830 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1490 reflections with I > 2σ(I) |
Tmin = 0.748, Tmax = 0.861 | Rint = 0.062 |
8028 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.87 e Å−3 |
2830 reflections | Δρmin = −0.37 e Å−3 |
183 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 | ||
Br1 | 0.81952 (14) | 1.00196 (2) | 0.69361 (11) | 0.0935 (4) | |
O1 | 0.6647 (7) | 0.79484 (14) | 0.7321 (5) | 0.0613 (11) | |
H1 | 0.6183 | 0.7820 | 0.6365 | 0.092* | |
O2 | 0.3297 (6) | 0.70963 (13) | 0.4419 (5) | 0.0602 (11) | |
N1 | 0.4384 (6) | 0.79657 (14) | 0.4079 (5) | 0.0391 (10) | |
N2 | 0.3180 (6) | 0.76994 (15) | 0.2660 (5) | 0.0416 (10) | |
H2 | 0.2720 | 0.7810 | 0.1620 | 0.050* | |
C1 | 0.6935 (8) | 0.84139 (19) | 0.7143 (6) | 0.0442 (13) | |
C2 | 0.6016 (8) | 0.86503 (17) | 0.5556 (6) | 0.0390 (12) | |
C3 | 0.6426 (8) | 0.91292 (19) | 0.5540 (7) | 0.0497 (14) | |
H3 | 0.5829 | 0.9294 | 0.4491 | 0.060* | |
C4 | 0.7677 (8) | 0.9363 (2) | 0.7018 (8) | 0.0555 (15) | |
C5 | 0.8592 (10) | 0.9132 (2) | 0.8592 (8) | 0.0655 (17) | |
H5 | 0.9461 | 0.9293 | 0.9598 | 0.079* | |
C6 | 0.8202 (9) | 0.8661 (2) | 0.8654 (8) | 0.0658 (18) | |
H6 | 0.8789 | 0.8503 | 0.9716 | 0.079* | |
C7 | 0.4633 (7) | 0.84066 (17) | 0.3902 (6) | 0.0370 (12) | |
C8 | 0.2737 (8) | 0.72504 (18) | 0.2962 (7) | 0.0430 (13) | |
C9 | 0.1524 (8) | 0.69622 (19) | 0.1385 (7) | 0.0460 (13) | |
C10 | 0.0099 (8) | 0.7153 (2) | −0.0181 (7) | 0.0509 (14) | |
H10 | −0.0132 | 0.7477 | −0.0273 | 0.061* | |
C11 | −0.0978 (9) | 0.6865 (2) | −0.1603 (8) | 0.0581 (16) | |
H11 | −0.1931 | 0.6994 | −0.2649 | 0.070* | |
C12 | −0.0621 (10) | 0.6383 (2) | −0.1449 (9) | 0.0641 (17) | |
H12 | −0.1335 | 0.6186 | −0.2400 | 0.077* | |
C13 | 0.0790 (11) | 0.6191 (2) | 0.0110 (9) | 0.0618 (16) | |
H13 | 0.1027 | 0.5866 | 0.0200 | 0.074* | |
C14 | 0.1832 (9) | 0.64743 (19) | 0.1507 (7) | 0.0496 (14) | |
H14 | 0.2760 | 0.6342 | 0.2557 | 0.060* | |
C15 | 0.3682 (9) | 0.86765 (19) | 0.2249 (6) | 0.0535 (15) | |
H15A | 0.4673 | 0.8733 | 0.1836 | 0.080* | |
H15B | 0.3186 | 0.8973 | 0.2445 | 0.080* | |
H15C | 0.2571 | 0.8498 | 0.1395 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.1011 (7) | 0.0462 (5) | 0.0962 (7) | −0.0133 (4) | 0.0123 (5) | −0.0172 (4) |
O1 | 0.073 (3) | 0.058 (3) | 0.040 (2) | −0.003 (2) | 0.014 (2) | 0.0092 (19) |
O2 | 0.103 (3) | 0.040 (2) | 0.041 (2) | 0.000 (2) | 0.037 (2) | 0.0038 (17) |
N1 | 0.051 (3) | 0.036 (3) | 0.029 (2) | 0.002 (2) | 0.0173 (19) | −0.0012 (19) |
N2 | 0.054 (3) | 0.037 (3) | 0.032 (2) | −0.006 (2) | 0.019 (2) | −0.0022 (19) |
C1 | 0.043 (3) | 0.045 (3) | 0.037 (3) | −0.003 (2) | 0.011 (2) | 0.004 (2) |
C2 | 0.034 (3) | 0.039 (3) | 0.044 (3) | 0.002 (2) | 0.017 (2) | −0.005 (2) |
C3 | 0.047 (3) | 0.049 (3) | 0.040 (3) | 0.008 (3) | 0.009 (3) | −0.005 (3) |
C4 | 0.047 (3) | 0.048 (4) | 0.062 (4) | 0.001 (3) | 0.015 (3) | −0.014 (3) |
C5 | 0.064 (4) | 0.067 (4) | 0.051 (4) | −0.005 (3) | 0.013 (3) | −0.020 (3) |
C6 | 0.062 (4) | 0.079 (5) | 0.040 (3) | 0.002 (3) | 0.008 (3) | −0.003 (3) |
C7 | 0.044 (3) | 0.037 (3) | 0.028 (3) | 0.004 (2) | 0.014 (2) | −0.001 (2) |
C8 | 0.064 (4) | 0.032 (3) | 0.041 (3) | 0.006 (3) | 0.031 (3) | 0.000 (2) |
C9 | 0.057 (3) | 0.043 (3) | 0.049 (3) | −0.009 (3) | 0.033 (3) | −0.004 (3) |
C10 | 0.057 (3) | 0.040 (3) | 0.053 (4) | −0.006 (3) | 0.022 (3) | 0.004 (3) |
C11 | 0.058 (4) | 0.052 (4) | 0.055 (4) | −0.013 (3) | 0.017 (3) | −0.006 (3) |
C12 | 0.070 (4) | 0.062 (4) | 0.064 (4) | −0.024 (3) | 0.034 (4) | −0.027 (3) |
C13 | 0.082 (4) | 0.041 (3) | 0.079 (5) | −0.009 (3) | 0.050 (4) | −0.011 (3) |
C14 | 0.066 (4) | 0.036 (3) | 0.053 (3) | −0.004 (3) | 0.033 (3) | −0.003 (3) |
C15 | 0.071 (4) | 0.036 (3) | 0.034 (3) | 0.001 (3) | 0.006 (3) | 0.002 (2) |
Br1—C4 | 1.902 (6) | C6—H6 | 0.9300 |
O1—C1 | 1.353 (6) | C7—C15 | 1.482 (7) |
O1—H1 | 0.8200 | C8—C9 | 1.485 (7) |
O2—C8 | 1.210 (6) | C9—C10 | 1.389 (7) |
N1—C7 | 1.279 (6) | C9—C14 | 1.394 (7) |
N1—N2 | 1.366 (5) | C10—C11 | 1.382 (7) |
N2—C8 | 1.365 (6) | C10—H10 | 0.9300 |
N2—H2 | 0.8600 | C11—C12 | 1.384 (8) |
C1—C2 | 1.391 (7) | C11—H11 | 0.9300 |
C1—C6 | 1.397 (8) | C12—C13 | 1.383 (9) |
C2—C3 | 1.389 (7) | C12—H12 | 0.9300 |
C2—C7 | 1.492 (7) | C13—C14 | 1.358 (8) |
C3—C4 | 1.358 (7) | C13—H13 | 0.9300 |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.376 (8) | C15—H15A | 0.9600 |
C5—C6 | 1.367 (9) | C15—H15B | 0.9600 |
C5—H5 | 0.9300 | C15—H15C | 0.9600 |
C1—O1—H1 | 109.5 | O2—C8—C9 | 122.1 (5) |
C7—N1—N2 | 120.1 (4) | N2—C8—C9 | 115.7 (4) |
C8—N2—N1 | 117.2 (4) | C10—C9—C14 | 118.9 (5) |
C8—N2—H2 | 121.4 | C10—C9—C8 | 123.5 (5) |
N1—N2—H2 | 121.4 | C14—C9—C8 | 117.6 (5) |
O1—C1—C2 | 123.2 (4) | C11—C10—C9 | 120.7 (6) |
O1—C1—C6 | 117.0 (5) | C11—C10—H10 | 119.6 |
C2—C1—C6 | 119.8 (5) | C9—C10—H10 | 119.6 |
C3—C2—C1 | 117.8 (5) | C10—C11—C12 | 119.1 (6) |
C3—C2—C7 | 119.9 (4) | C10—C11—H11 | 120.4 |
C1—C2—C7 | 122.3 (5) | C12—C11—H11 | 120.4 |
C4—C3—C2 | 121.6 (5) | C13—C12—C11 | 120.4 (5) |
C4—C3—H3 | 119.2 | C13—C12—H12 | 119.8 |
C2—C3—H3 | 119.2 | C11—C12—H12 | 119.8 |
C3—C4—C5 | 120.9 (6) | C14—C13—C12 | 120.2 (6) |
C3—C4—Br1 | 120.2 (5) | C14—C13—H13 | 119.9 |
C5—C4—Br1 | 118.9 (4) | C12—C13—H13 | 119.9 |
C6—C5—C4 | 118.9 (6) | C13—C14—C9 | 120.7 (6) |
C6—C5—H5 | 120.6 | C13—C14—H14 | 119.7 |
C4—C5—H5 | 120.6 | C9—C14—H14 | 119.7 |
C5—C6—C1 | 121.0 (6) | C7—C15—H15A | 109.5 |
C5—C6—H6 | 119.5 | C7—C15—H15B | 109.5 |
C1—C6—H6 | 119.5 | H15A—C15—H15B | 109.5 |
N1—C7—C15 | 125.8 (4) | C7—C15—H15C | 109.5 |
N1—C7—C2 | 114.2 (4) | H15A—C15—H15C | 109.5 |
C15—C7—C2 | 120.0 (5) | H15B—C15—H15C | 109.5 |
O2—C8—N2 | 122.2 (5) | ||
C7—N1—N2—C8 | −170.7 (5) | C1—C2—C7—N1 | −0.3 (7) |
O1—C1—C2—C3 | 179.8 (5) | C3—C2—C7—C15 | −0.6 (7) |
C6—C1—C2—C3 | 0.8 (8) | C1—C2—C7—C15 | 179.6 (5) |
O1—C1—C2—C7 | −0.4 (8) | N1—N2—C8—O2 | 3.3 (7) |
C6—C1—C2—C7 | −179.4 (5) | N1—N2—C8—C9 | −176.6 (4) |
C1—C2—C3—C4 | −0.2 (8) | O2—C8—C9—C10 | 149.0 (5) |
C7—C2—C3—C4 | −180.0 (5) | N2—C8—C9—C10 | −31.1 (7) |
C2—C3—C4—C5 | 0.2 (9) | O2—C8—C9—C14 | −30.3 (8) |
C2—C3—C4—Br1 | −180.0 (4) | N2—C8—C9—C14 | 149.6 (5) |
C3—C4—C5—C6 | −0.8 (9) | C14—C9—C10—C11 | −0.8 (8) |
Br1—C4—C5—C6 | 179.3 (5) | C8—C9—C10—C11 | 179.9 (5) |
C4—C5—C6—C1 | 1.5 (10) | C9—C10—C11—C12 | 0.0 (8) |
O1—C1—C6—C5 | 179.4 (6) | C10—C11—C12—C13 | 0.3 (9) |
C2—C1—C6—C5 | −1.5 (9) | C11—C12—C13—C14 | 0.3 (9) |
N2—N1—C7—C15 | 1.2 (8) | C12—C13—C14—C9 | −1.2 (9) |
N2—N1—C7—C2 | −178.9 (4) | C10—C9—C14—C13 | 1.4 (8) |
C3—C2—C7—N1 | 179.5 (5) | C8—C9—C14—C13 | −179.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.85 | 2.522 (6) | 138 |
N2—H2···O2i | 0.86 | 2.14 | 2.889 (6) | 146 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H13BrN2O2 |
Mr | 333.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.3761 (15), 28.270 (6), 8.6089 (13) |
β (°) | 116.928 (12) |
V (Å3) | 1600.5 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.57 |
Crystal size (mm) | 0.12 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.748, 0.861 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8028, 2830, 1490 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.188, 1.01 |
No. of reflections | 2830 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.87, −0.37 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.820 | 1.854 | 2.522 (6) | 137.71 |
N2—H2···O2i | 0.860 | 2.138 | 2.889 (6) | 145.55 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Acknowledgements
This project was supported by the Postgraduate Foundation of Xi'an Polytechnic University (grant No. Y05–2–09)
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The chemistry of aroylhydrazones continues to attract much attention due to their coordination ability to metal ions (Singh et al., 1982; Salem, 1998) and their biological activity (Singh et al., 1982; Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives, the title compound was synthesized and its crystal structure is reported here.
The title molecule displays a trans configured C=N double bond (Fig. 1). The crystal structure is stabilized by intramolecular O—H···O and intermolecular N—H···O hydrogen bonds (Table 1. and Fig. 2).