3,5-Dibromo-2-hydroxy­benzaldehyde

Fan, Y.; You, W.; Qian, H.-F.; Liu, J.-L.; Huang, W.

doi:10.1107/S1600536808008726

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o799

doi:10.1107/S1600536808008726

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3,5-Dibromo-2-hydroxybenzaldehyde

Ying Fan,^a Wei You,^a Hui-Fen Qian,^a Jian-Lan Liu ^a ^* and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, Nanjing University-Jinchuan Group Ltd Joint Laboratory of Metal Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: njutljl@163.com, whuang@nju.edu.cn

(Received 5 March 2008; accepted 1 April 2008; online 4 April 2008)

The title compound, C₇H₄Br₂O₂, exhibits a layer packing structure via weak π–π stacking interactions [centroid–centroid distances between adjacent aromatic rings are 4.040 (8) and 3.776 (7) Å]. Molecules in each layer are linked by intermolecular O—H⋯O hydrogen bonding and Br⋯Br interactions [3.772 (4) Å]. There are two molecules in the asymmetric unit.

Related literature

For related compounds, see Harkat et al. (2008 ); Lu et al. (2006 ); Duan et al. (2007 ); Zhang et al. (2007 ).

Experimental

Crystal data

C₇H₄Br₂O₂
M_r = 279.92
Monoclinic, P 2₁ /c
a = 16.474 (8) Å
b = 14.025 (10) Å
c = 7.531 (7) Å
β = 103.212 (2)°
V = 1694 (2) Å³
Z = 8
Mo Kα radiation
μ = 9.52 mm⁻¹
T = 291 (2) K
0.10 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.450, T_max = 0.450 (expected range = 0.386–0.386)
8777 measured reflections
3328 independent reflections
1670 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.105
S = 0.79
3328 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.82	1.94	2.660 (6)	146
O4—H4A⋯O3	0.82	2.01	2.713 (6)	143
O4—H4A⋯O1ⁱ	0.82	2.29	2.863 (6)	128
C7—H7⋯O3ⁱⁱ	0.93	2.55	3.122 (8)	120
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808008726/at2547sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008726/at2547Isup2.hkl

checkCIF report

Comment top

Slicylaldehyde and its derivatives are an important class of compounds which can be used in a variety of studies such as organic synthesis, catalyst, drug design, spicery industry and life science and so on (Harkat et al., 2008). In the past few decades, a continuing attention has been drawn to the derivatives of the salicylaldehyde and their metal complexes for the investigation of luminescent properties which could be finely tuned by different substituent groups bonded to the phenolic ring (Lu et al., 2006; Duan et al., 2007; Zhang et al., 2007). In this paper, we report the X-ray structure of 3,5-dibromo-2-hydroxybenzaldehyde, (I).

The molecular structure of (I) is illustrated in Fig. 1. There are two crystallographically independent molecules in the asymmetric unit, and both of them are essentially planar with the dihedral angle of 1.82 (6)°.

The C—H···O and O—H···O hydrogen bonding interactions contribute to the stabilizations of the molecular and crystal structures (Fig. 2 and Table 1). A layer packing structure is formed with the mean interlayer separation of 4.040 (8) and 3.776 (7) Å for two sets of molecules. The centeroid-to-centeriod separations between the adjacent aromatic rings are 4.040 (8) and 3.776 (7) Å, respectively (Fig. 3), indicative of weak π–π stacking interactions.

Related literature top

For related compounds, see Harkat et al. (2008); Lu et al. (2006); Duan et al. (2007); Zhang et al. (2007).

Experimental top

The title compound was obtained as received. Single crystals suitable for X-ray diffraction measurement were formed after 5 days in ethyl acetate by slow evaporation at room temperature in air. Analysis calculated for C₇H₄O₄Br₂: C 30.04, H 1.44%. Found: C 30.08, H 1.39%. FT—IR (KBr pellets, cm^-1): 3180(m), 3069(m), 1681(versus), 1662(versus), 1597(m), 1448(s), 1408(s), 1281(versus), 1198(s), 1151(m), 1134(m), 1098(m), 919(s), 877(s), 712(m) and 677(s).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A perspective view of the intralayer intermolecular hydrogen-bond contacts among molecules in the title compound. Hydrogen bonds and Br–Br interactions are shown as dashed lines. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 1/2; (ii) - x + 1,-1/2 + y, 1/2 - z; (iii) x, -1 + y, z.]
	Fig. 3. A perspective view of the interlayer π–π stacking interactions together with the centroid–centroid contacts.

3,5-Dibromo-2-hydroxybenzaldehyde top

Crystal data top

C₇H₄Br₂O₂	F(000) = 1056
M_r = 279.92	D_x = 2.195 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1688 reflections
a = 16.474 (8) Å	θ = 2.9–22.8°
b = 14.025 (10) Å	µ = 9.52 mm⁻¹
c = 7.531 (7) Å	T = 291 K
β = 103.212 (2)°	Block, yellow
V = 1694 (2) Å³	0.10 × 0.10 × 0.10 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	3328 independent reflections
Radiation source: fine-focus sealed tube	1670 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −20→15
T_min = 0.450, T_max = 0.450	k = −17→16
8777 measured reflections	l = −7→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0451P)²] where P = (F_o² + 2F_c²)/3
S = 0.79	(Δ/σ)_max < 0.001
3328 reflections	Δρ_max = 0.67 e Å⁻³
202 parameters	Δρ_min = −0.55 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (3)

Crystal data top

C₇H₄Br₂O₂	V = 1694 (2) Å³
M_r = 279.92	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.474 (8) Å	µ = 9.52 mm⁻¹
b = 14.025 (10) Å	T = 291 K
c = 7.531 (7) Å	0.10 × 0.10 × 0.10 mm
β = 103.212 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3328 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1670 reflections with I > 2σ(I)
T_min = 0.450, T_max = 0.450	R_int = 0.109
8777 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 0.79	Δρ_max = 0.67 e Å⁻³
3328 reflections	Δρ_min = −0.55 e Å⁻³
202 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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	0.33358 (5)	0.40384 (5)	0.34454 (11)	0.0666 (3)
Br2	0.32451 (4)	−0.00188 (5)	0.34528 (10)	0.0653 (3)
Br3	0.10268 (5)	0.96790 (5)	0.39100 (13)	0.0750 (3)
Br4	−0.12580 (4)	0.67358 (6)	0.46512 (11)	0.0727 (3)
C1	0.5095 (4)	0.1950 (4)	0.3046 (8)	0.0424 (15)
C2	0.4701 (4)	0.2838 (4)	0.3143 (8)	0.0455 (16)
C3	0.3876 (4)	0.2848 (5)	0.3376 (8)	0.0490 (17)
C4	0.3467 (4)	0.2004 (5)	0.3511 (9)	0.0539 (18)
H4	0.2925	0.2016	0.3681	0.065*
C5	0.3858 (4)	0.1130 (5)	0.3396 (8)	0.0504 (17)
C6	0.4670 (4)	0.1100 (5)	0.3151 (8)	0.0488 (17)
H6	0.4927	0.0518	0.3059	0.059*
C7	0.5945 (4)	0.1906 (5)	0.2718 (9)	0.0574 (19)
H7	0.6177	0.1306	0.2649	0.069*
C8	0.1215 (4)	0.6721 (5)	0.4036 (9)	0.0494 (17)
C9	0.1402 (4)	0.7692 (5)	0.3912 (8)	0.0456 (16)
C10	0.0787 (4)	0.8359 (4)	0.4063 (8)	0.0477 (17)
C11	0.0001 (4)	0.8089 (5)	0.4295 (9)	0.0542 (18)
H11	−0.0393	0.8548	0.4395	0.065*
C12	−0.0188 (4)	0.7110 (5)	0.4376 (9)	0.0510 (18)
C13	0.0415 (4)	0.6440 (5)	0.4260 (8)	0.0518 (17)
H13	0.0294	0.5795	0.4329	0.062*
C14	0.1838 (5)	0.5982 (5)	0.3899 (10)	0.066 (2)
H14	0.1689	0.5349	0.4011	0.079*
O1	0.6364 (3)	0.2604 (3)	0.2531 (7)	0.0702 (15)
O2	0.5114 (3)	0.3678 (3)	0.3080 (7)	0.0655 (13)
H2	0.5587	0.3568	0.2960	0.098*
O3	0.2528 (3)	0.6135 (3)	0.3652 (8)	0.0762 (15)
O4	0.2139 (2)	0.8015 (3)	0.3645 (7)	0.0563 (12)
H4A	0.2422	0.7563	0.3452	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0687 (5)	0.0551 (5)	0.0819 (6)	0.0197 (4)	0.0292 (4)	0.0055 (4)
Br2	0.0571 (5)	0.0538 (5)	0.0879 (6)	−0.0152 (4)	0.0226 (4)	−0.0017 (4)
Br3	0.0666 (5)	0.0371 (5)	0.1317 (8)	0.0011 (4)	0.0441 (5)	−0.0014 (5)
Br4	0.0484 (5)	0.0764 (6)	0.0966 (6)	−0.0142 (4)	0.0233 (4)	0.0000 (5)
C1	0.041 (4)	0.039 (4)	0.048 (4)	−0.005 (3)	0.012 (3)	0.000 (3)
C2	0.054 (4)	0.034 (4)	0.049 (4)	−0.005 (3)	0.012 (3)	0.004 (3)
C3	0.048 (4)	0.051 (5)	0.047 (4)	0.010 (3)	0.010 (3)	−0.001 (4)
C4	0.043 (4)	0.060 (5)	0.060 (4)	−0.003 (4)	0.016 (3)	−0.004 (4)
C5	0.050 (4)	0.049 (5)	0.054 (4)	−0.007 (3)	0.015 (3)	−0.008 (4)
C6	0.040 (4)	0.046 (4)	0.060 (5)	−0.003 (3)	0.011 (3)	0.001 (4)
C7	0.050 (4)	0.046 (5)	0.078 (5)	0.008 (3)	0.018 (4)	0.006 (4)
C8	0.053 (4)	0.041 (4)	0.055 (4)	−0.004 (3)	0.014 (3)	0.003 (3)
C9	0.043 (4)	0.046 (4)	0.049 (4)	0.001 (3)	0.011 (3)	−0.001 (3)
C10	0.049 (4)	0.041 (4)	0.055 (4)	−0.002 (3)	0.015 (3)	−0.001 (3)
C11	0.049 (4)	0.056 (5)	0.059 (4)	0.002 (4)	0.016 (3)	−0.005 (4)
C12	0.041 (4)	0.063 (5)	0.052 (4)	0.001 (3)	0.018 (3)	0.007 (4)
C13	0.053 (4)	0.042 (4)	0.062 (5)	−0.010 (3)	0.017 (3)	0.005 (4)
C14	0.077 (6)	0.035 (4)	0.091 (6)	0.013 (4)	0.028 (5)	0.011 (4)
O1	0.049 (3)	0.052 (3)	0.116 (4)	−0.002 (3)	0.032 (3)	0.010 (3)
O2	0.057 (3)	0.045 (3)	0.098 (4)	0.001 (2)	0.026 (3)	0.004 (3)
O3	0.059 (3)	0.049 (3)	0.130 (5)	0.013 (3)	0.043 (3)	0.013 (3)
O4	0.037 (3)	0.041 (3)	0.097 (4)	0.001 (2)	0.029 (2)	−0.002 (3)

Geometric parameters (Å, º) top

Br1—C3	1.898 (6)	C7—H7	0.9300
Br2—C5	1.906 (6)	C8—C9	1.404 (9)
Br3—C10	1.902 (6)	C8—C13	1.424 (8)
Br4—C12	1.895 (6)	C8—C14	1.479 (9)
C1—C6	1.394 (8)	C9—O4	1.355 (7)
C1—C2	1.413 (8)	C9—C10	1.402 (8)
C1—C7	1.477 (8)	C10—C11	1.398 (8)
C2—O2	1.368 (7)	C11—C12	1.412 (9)
C2—C3	1.410 (8)	C11—H11	0.9300
C3—C4	1.377 (8)	C12—C13	1.384 (8)
C4—C5	1.397 (8)	C13—H13	0.9300
C4—H4	0.9300	C14—O3	1.213 (8)
C5—C6	1.393 (8)	C14—H14	0.9300
C6—H6	0.9300	O2—H2	0.8200
C7—O1	1.225 (7)	O4—H4A	0.8200

C6—C1—C2	120.5 (6)	C9—C8—C14	120.7 (6)
C6—C1—C7	118.7 (6)	C13—C8—C14	119.4 (6)
C2—C1—C7	120.7 (6)	O4—C9—C10	118.6 (6)
O2—C2—C3	119.8 (6)	O4—C9—C8	123.5 (6)
O2—C2—C1	121.3 (6)	C10—C9—C8	118.0 (6)
C3—C2—C1	118.9 (6)	C11—C10—C9	122.4 (6)
C4—C3—C2	120.2 (6)	C11—C10—Br3	118.9 (5)
C4—C3—Br1	120.9 (5)	C9—C10—Br3	118.7 (5)
C2—C3—Br1	118.9 (5)	C10—C11—C12	119.3 (6)
C3—C4—C5	120.6 (6)	C10—C11—H11	120.4
C3—C4—H4	119.7	C12—C11—H11	120.4
C5—C4—H4	119.7	C13—C12—C11	119.3 (6)
C6—C5—C4	120.3 (6)	C13—C12—Br4	121.2 (5)
C6—C5—Br2	120.5 (5)	C11—C12—Br4	119.6 (5)
C4—C5—Br2	119.1 (5)	C12—C13—C8	121.1 (6)
C5—C6—C1	119.5 (6)	C12—C13—H13	119.4
C5—C6—H6	120.2	C8—C13—H13	119.4
C1—C6—H6	120.2	O3—C14—C8	125.1 (7)
O1—C7—C1	124.5 (6)	O3—C14—H14	117.4
O1—C7—H7	117.7	C8—C14—H14	117.4
C1—C7—H7	117.7	C2—O2—H2	109.5
C9—C8—C13	119.9 (6)	C9—O4—H4A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.94	2.660 (6)	146
O4—H4A···O3	0.82	2.01	2.713 (6)	143
O4—H4A···O1ⁱ	0.82	2.29	2.863 (6)	128
C7—H7···O3ⁱⁱ	0.93	2.55	3.122 (8)	120

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₄Br₂O₂
M_r	279.92
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	16.474 (8), 14.025 (10), 7.531 (7)
β (°)	103.212 (2)
V (Å³)	1694 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	9.52
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.450, 0.450
No. of measured, independent and observed [I > 2σ(I)] reflections	8777, 3328, 1670
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.106, 0.79
No. of reflections	3328
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.55

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Br1—C3	1.898 (6)	C2—O2	1.368 (7)
Br2—C5	1.906 (6)	C7—O1	1.225 (7)
Br3—C10	1.902 (6)	C9—O4	1.355 (7)
Br4—C12	1.895 (6)	C14—O3	1.213 (8)

O1—C7—C1	124.5 (6)	O3—C14—C8	125.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.94	2.660 (6)	146.2
O4—H4A···O3	0.82	2.01	2.713 (6)	143.1
O4—H4A···O1ⁱ	0.82	2.29	2.863 (6)	127.8
C7—H7···O3ⁱⁱ	0.93	2.55	3.122 (8)	119.8

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (No. 20301009) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for financial support.

References

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