2,4-Dibromo-6-[(hydroxyimino)methyl]phenol

Luo, Y.-H.; Xu, J.; Pan, M.-L.; Li, J.-F.

doi:10.1107/S1600536811028741

organic compounds

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doi:10.1107/S1600536811028741

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2,4-Dibromo-6-[(hydroxyimino)methyl]phenol

Yang-Hui Luo,^a ^* Jian Xu,^a Mei-Ling Pan ^a and Jin-Feng Li ^a

^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

(Received 13 July 2011; accepted 17 July 2011; online 23 July 2011)

In the title compound, C₇H₅Br₄NO₂, intramolecular O—H⋯N hydrogen bonds are observed. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the molecules into dimers.

Related literature

For details of the preparation, see: Dey et al. (2003 ).

Experimental

Crystal data

C₇H₅Br₂NO₂
M_r = 294.94
Triclinic, $[P \overline 1]$
a = 4.2590 (5) Å
b = 8.6742 (7) Å
c = 12.0831 (11) Å
α = 74.171 (1)°
β = 82.248 (2)°
γ = 79.028 (1)°
V = 419.98 (7) Å³
Z = 2
Mo Kα radiation
μ = 9.60 mm⁻¹
T = 293 K
0.80 × 0.42 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.048, T_max = 0.277
2162 measured reflections
1453 independent reflections
987 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.160
S = 1.05
1453 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 1.50 e Å⁻³
Δρ_min = −1.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028741/jh2311sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028741/jh2311Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028741/jh2311Isup3.cml

checkCIF report

Comment top

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).

Related literature top

For details of the preparation, see: Dey et al. (2003).

Experimental top

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.

Computing details top

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: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Intramolecular hydrogen bonds are shown as dashed line.
	Fig. 2. A packing view down the a axis showing the three dimensional network.Intermolecular hydrogen bonds are shown as dashed lines. Intramolecular O—H···N hydrogen bonds have been omitted for the sake of clarity.

2,4-Dibromo-6-[(hydroxyimino)methyl]phenol top

Crystal data top

C₇H₅Br₂NO₂	Z = 2
M_r = 294.94	F(000) = 280
Triclinic, P1	D_x = 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

Data collection top

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	R_int = 0.037
Detector resolution: 8.192 pixels mm^-1	θ_max = 25.0°, θ_min = 2.5°
ϕ and ω scans	h = −5→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→10
T_min = 0.048, T_max = 0.277	l = −13→14
2162 measured reflections

Refinement top

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(F_o²) + (0.0812P)²] where P = (F_o² + 2F_c²)/3
1453 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 1.50 e Å⁻³
0 restraints	Δρ_min = −1.30 e Å⁻³

Crystal data top

C₇H₅Br₂NO₂	γ = 79.028 (1)°
M_r = 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)°

Data collection top

Rigaku R-AXIS RAPID CCD area-detector diffractometer	1453 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	987 reflections with I > 2σ(I)
T_min = 0.048, T_max = 0.277	R_int = 0.037
2162 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.05	Δρ_max = 1.50 e Å⁻³
1453 reflections	Δρ_min = −1.30 e Å⁻³
109 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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.048, 0.277
No. of measured, independent and observed [I > 2σ(I)] reflections	2162, 1453, 987
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2099

doi:10.1107/S1600536811028741

Open

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