organic compounds
2,4-Dibromo-6-[(hydroxyimino)methyl]phenol
aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: chmsunbw@seu.edu.cn
In the title compound, C7H5Br4NO2, intramolecular O—H⋯N hydrogen bonds are observed. In the intermolecular O—H⋯O hydrogen bonds link the molecules into dimers.
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536811028741/jh2311sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811028741/jh2311Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811028741/jh2311Isup3.cml
3,5-dibromosalicylaldoxime were synthesized as follows: 0.2 mol (13.9 g) hydroxylamine hydrochloride in companied with 0.2 mol (8 g) NaOH were dissolved in 50 ml ethanol solution in a 250 ml round bottomed flask and stirred to homogeneous. After that, an ethanol solution (30 ml) with 0.2 mol (40 g) 3,5-dibromosalicylicaldehyde was added dropwise to this solution at 70 °C and refluxed for about 2 h. After cooling and filtrating, crude compound of 3,5-dibromosalicylaldoximewas gained. Pure compound of it was obtained by crystallizing from 20 ml ethanol solution (Dey, et al., 2003).
Crystals of 3,5-dibromosalicylaldoxime suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution.
All H atoms attached to C atoms and O atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (CH) and O—H = 0.82 Å with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O).
Data collection: CrystalClear (Rigaku, 2005); cell
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: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C7H5Br2NO2 | Z = 2 |
Mr = 294.94 | F(000) = 280 |
Triclinic, P1 | Dx = 2.332 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.2590 (5) Å | Cell parameters from 808 reflections |
b = 8.6742 (7) Å | θ = 2.5–26.6° |
c = 12.0831 (11) Å | µ = 9.60 mm−1 |
α = 74.171 (1)° | T = 293 K |
β = 82.248 (2)° | Prism, white |
γ = 79.028 (1)° | 0.80 × 0.42 × 0.18 mm |
V = 419.98 (7) Å3 |
Rigaku R-AXIS RAPID CCD area-detector diffractometer | 1453 independent reflections |
Radiation source: fine-focus sealed tube | 987 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.192 pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
ϕ and ω scans | h = −5→5 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −9→10 |
Tmin = 0.048, Tmax = 0.277 | l = −13→14 |
2162 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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0812P)2] where P = (Fo2 + 2Fc2)/3 |
1453 reflections | (Δ/σ)max = 0.001 |
109 parameters | Δρmax = 1.50 e Å−3 |
0 restraints | Δρmin = −1.30 e Å−3 |
C7H5Br2NO2 | γ = 79.028 (1)° |
Mr = 294.94 | V = 419.98 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.2590 (5) Å | Mo Kα radiation |
b = 8.6742 (7) Å | µ = 9.60 mm−1 |
c = 12.0831 (11) Å | T = 293 K |
α = 74.171 (1)° | 0.80 × 0.42 × 0.18 mm |
β = 82.248 (2)° |
Rigaku R-AXIS RAPID CCD area-detector diffractometer | 1453 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 987 reflections with I > 2σ(I) |
Tmin = 0.048, Tmax = 0.277 | Rint = 0.037 |
2162 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.50 e Å−3 |
1453 reflections | Δρmin = −1.30 e Å−3 |
109 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 | 0.3846 (3) | 0.03675 (11) | 1.18327 (9) | 0.0501 (4) | |
Br2 | 0.1284 (3) | 0.71718 (11) | 1.09089 (9) | 0.0508 (4) | |
N1 | 0.9050 (19) | 0.2301 (9) | 1.5027 (7) | 0.040 (2) | |
O1 | 1.0649 (17) | 0.2544 (8) | 1.5855 (6) | 0.0474 (18) | |
H1 | 1.1377 | 0.1664 | 1.6269 | 0.071* | |
O2 | 0.6873 (17) | 0.0731 (7) | 1.3820 (6) | 0.0469 (18) | |
H2 | 0.7721 | 0.0846 | 1.4357 | 0.070* | |
C1 | 0.783 (2) | 0.3610 (10) | 1.4352 (8) | 0.037 (2) | |
H1A | 0.8077 | 0.4594 | 1.4471 | 0.045* | |
C2 | 0.609 (2) | 0.3625 (10) | 1.3421 (8) | 0.031 (2) | |
C3 | 0.575 (2) | 0.2192 (10) | 1.3157 (7) | 0.030 (2) | |
C4 | 0.424 (2) | 0.2277 (10) | 1.2216 (8) | 0.036 (2) | |
C5 | 0.287 (2) | 0.3756 (11) | 1.1518 (8) | 0.040 (2) | |
H5 | 0.1827 | 0.3798 | 1.0881 | 0.048* | |
C6 | 0.314 (2) | 0.5157 (10) | 1.1813 (8) | 0.036 (2) | |
C7 | 0.477 (2) | 0.5089 (11) | 1.2733 (8) | 0.038 (2) | |
H7 | 0.4994 | 0.6049 | 1.2896 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0685 (8) | 0.0273 (6) | 0.0611 (8) | −0.0064 (5) | −0.0103 (6) | −0.0208 (5) |
Br2 | 0.0661 (8) | 0.0263 (6) | 0.0574 (8) | 0.0040 (5) | −0.0175 (5) | −0.0084 (5) |
N1 | 0.044 (5) | 0.031 (4) | 0.048 (5) | −0.005 (4) | −0.002 (4) | −0.016 (4) |
O1 | 0.063 (5) | 0.026 (3) | 0.058 (5) | 0.004 (3) | −0.025 (4) | −0.017 (3) |
O2 | 0.067 (5) | 0.019 (3) | 0.055 (4) | 0.003 (3) | −0.015 (4) | −0.012 (3) |
C1 | 0.031 (5) | 0.024 (5) | 0.055 (6) | 0.003 (4) | −0.005 (4) | −0.012 (5) |
C2 | 0.022 (5) | 0.026 (5) | 0.048 (6) | 0.002 (4) | −0.002 (4) | −0.017 (4) |
C3 | 0.038 (5) | 0.021 (4) | 0.030 (5) | −0.001 (4) | −0.003 (4) | −0.008 (4) |
C4 | 0.037 (5) | 0.022 (5) | 0.051 (6) | −0.003 (4) | 0.004 (5) | −0.019 (4) |
C5 | 0.043 (6) | 0.040 (6) | 0.040 (6) | −0.008 (5) | −0.006 (5) | −0.014 (5) |
C6 | 0.044 (6) | 0.026 (5) | 0.038 (5) | −0.001 (4) | 0.001 (4) | −0.011 (4) |
C7 | 0.036 (6) | 0.025 (5) | 0.053 (6) | −0.008 (4) | 0.003 (5) | −0.013 (4) |
Br1—C4 | 1.879 (8) | C2—C7 | 1.377 (13) |
Br2—C6 | 1.882 (9) | C2—C3 | 1.402 (11) |
N1—C1 | 1.268 (12) | C3—C4 | 1.360 (13) |
N1—O1 | 1.364 (10) | C4—C5 | 1.397 (13) |
O1—H1 | 0.8200 | C5—C6 | 1.384 (12) |
O2—C3 | 1.339 (10) | C5—H5 | 0.9300 |
O2—H2 | 0.8200 | C6—C7 | 1.371 (13) |
C1—C2 | 1.424 (13) | C7—H7 | 0.9300 |
C1—H1A | 0.9300 | ||
C1—N1—O1 | 113.3 (7) | C3—C4—C5 | 122.1 (8) |
N1—O1—H1 | 109.5 | C3—C4—Br1 | 120.1 (7) |
C3—O2—H2 | 109.5 | C5—C4—Br1 | 117.8 (7) |
N1—C1—C2 | 122.3 (8) | C6—C5—C4 | 117.4 (9) |
N1—C1—H1A | 118.9 | C6—C5—H5 | 121.3 |
C2—C1—H1A | 118.9 | C4—C5—H5 | 121.3 |
C7—C2—C3 | 118.5 (9) | C7—C6—C5 | 121.0 (9) |
C7—C2—C1 | 119.4 (8) | C7—C6—Br2 | 120.3 (7) |
C3—C2—C1 | 122.0 (8) | C5—C6—Br2 | 118.7 (8) |
O2—C3—C4 | 119.1 (8) | C6—C7—C2 | 121.2 (8) |
O2—C3—C2 | 121.3 (8) | C6—C7—H7 | 119.4 |
C4—C3—C2 | 119.7 (8) | C2—C7—H7 | 119.4 |
O1—N1—C1—C2 | 179.2 (7) | C2—C3—C4—Br1 | 178.5 (6) |
N1—C1—C2—C7 | 178.8 (9) | C3—C4—C5—C6 | 0.6 (14) |
N1—C1—C2—C3 | −3.0 (14) | Br1—C4—C5—C6 | 179.4 (6) |
C7—C2—C3—O2 | −177.4 (8) | C4—C5—C6—C7 | 2.0 (14) |
C1—C2—C3—O2 | 4.4 (13) | C4—C5—C6—Br2 | −179.0 (7) |
C7—C2—C3—C4 | 2.2 (13) | C5—C6—C7—C2 | −2.5 (14) |
C1—C2—C3—C4 | −176.0 (8) | Br2—C6—C7—C2 | 178.6 (7) |
O2—C3—C4—C5 | 176.9 (8) | C3—C2—C7—C6 | 0.3 (13) |
C2—C3—C4—C5 | −2.7 (14) | C1—C2—C7—C6 | 178.6 (8) |
O2—C3—C4—Br1 | −1.9 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.10 | 2.775 (8) | 140 |
O2—H2···N1 | 0.82 | 1.88 | 2.601 (10) | 147 |
Symmetry code: (i) −x+2, −y, −z+3. |
Experimental details
Crystal data | |
Chemical formula | C7H5Br2NO2 |
Mr | 294.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 4.2590 (5), 8.6742 (7), 12.0831 (11) |
α, β, γ (°) | 74.171 (1), 82.248 (2), 79.028 (1) |
V (Å3) | 419.98 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 9.60 |
Crystal size (mm) | 0.80 × 0.42 × 0.18 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.048, 0.277 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2162, 1453, 987 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.160, 1.05 |
No. of reflections | 1453 |
No. of parameters | 109 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.50, −1.30 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 2.10 | 2.775 (8) | 140.0 |
O2—H2···N1 | 0.82 | 1.88 | 2.601 (10) | 146.7 |
Symmetry code: (i) −x+2, −y, −z+3. |
References
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge, Tennessee, U.S. Google Scholar
Dey, M., Rao, C. P., Saarenketo, P. K., Pissanen, K., Kolehmainen, E. & Guionneau, P. (2003). Polyhedron. 22, 3515–3521. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Rigaku. (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The derivatives of salicylaldehyde are important chemical materials, because they are excellent ligands for transition metals. As part of our interest in these ligands, we report here the crystal structure of the title compound.
The molecular structure of the title compound is shown in Fig. 1, where the dash line indicates the intramolecular O—H···N hydrogen bond.
All the non-H atoms of the title compound are located almost in one plane, as the atoms O1,O2 and N1 are shifted ca 0.1204 Å,0.0727Å and 0.0402Å out of the benzene ring plane, respectively.
The title compound formed dimer via intermolecular O—H···O hydrogen bonds and the dimers packed via π···π stacking interactions (3.4367 Å) (Fig. 2).