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In the crystal structure of the title compound, C8H5BrO3, two mol­ecules are linked about inversion centres by C—H...Br hydrogen bonds. The structure is also characterized by intra- and intermolecular hydrogen bonds between hydroxyl and aldehyde O atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013630/cv6044sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013630/cv6044Isup2.hkl
Contains datablock I

CCDC reference: 172221

Key indicators

  • Single-crystal X-ray study
  • T = 203 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.045
  • wR factor = 0.122
  • Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 26.78 From the CIF: _reflns_number_total 1476 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 1612 Completeness (_total/calc) 91.56% Alert C: < 95% complete RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.108 PLAT_725 Alert C D-H Calc 0.93(5), Rep 0.94100, Dev. 0.01 Ang. C7 -H7 1.555 1.555 PLAT_745 Alert C D-H Calc 0.89(7), Rep 0.89100 .... Missing s.u. O4 -H4 1.555 1.555 PLAT_745 Alert C D-H Calc 0.89(7), Rep 0.89100 .... Missing s.u. O4 -H4 1.555 1.555 PLAT_745 Alert C D-H Calc 1.00(5), Rep 1.00100 .... Missing s.u. C2 -H2 1.555 1.555 PLAT_745 Alert C D-H Calc 0.95(6), Rep 0.95400 .... Missing s.u. C6 -H6 1.555 1.555 PLAT_745 Alert C D-H Calc 0.93(5), Rep 0.94100 .... Missing s.u. C7 -H7 1.555 1.555 PLAT_746 Alert C H...A Calc 1.79(7), Rep 1.79100 .... Missing s.u. H4 -O8 1.555 1.555 PLAT_746 Alert C H...A Calc 2.47(7), Rep 2.47400 .... Missing s.u. H4 -O4 1.555 2.645 PLAT_746 Alert C H...A Calc 2.93(5), Rep 2.92700 .... Missing s.u. H2 -BR 1.555 3.665 PLAT_746 Alert C H...A Calc 2.57(6), Rep 2.56900 .... Missing s.u. H6 -O7 1.555 1.445 PLAT_746 Alert C H...A Calc 2.40(6), Rep 2.39500 .... Missing s.u. H7 -O4 1.555 1.555 PLAT_748 Alert C D-H..A Calc 151(7), Rep 151.47 .... Missing s.u. O4 -H4 -O8 1.555 1.555 1.555 PLAT_748 Alert C D-H..A Calc 104(4), Rep 104.17 .... Missing s.u. C7 -H7 -O4 1.555 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
15 Alert Level C = Please check

Comment top

5-Bromo-2-hydroxybenzene-1,3-dicarbaldehyde, (I), is a precursor in the synthesis of Robson-type ligands (Pilkington & Robson, 1970; Fenton, 1999). Bond lengths and angles are in the usual ranges. The molecule is planar with only minor distortions from the mean plane formed by non-H atoms; the deviations range from 0.004 (4) (for C6) to 0.126 (3) Å (O7). The crystal structure is also characterized by intra- and intermolecular hydrogen bonds (Table 1).

Experimental top

The title compound was synthesized according to previously reported methods (Taniguchi, 1984; Xie et al., 1994). To a solution of 4-bromo-2,6-dihydroxymethylphenol (40 g, 0.17 mol) in CHCl3 (1 l), MnO2 (232 g, 2.66 mol) was added. The resulting mixture was stirred under reflux for 48 h and cooled to room temperature. Then the solution was filtered and the solid was washed twice with 100 ml of CHCl3. The washings were added to the original filtrate and the combined solution was evaporated to yield a yellow solid (22 g, 55% yield). Crystals were obtained by the slow evaporation of a CHCl3 solution. 1H NMR (200 MHz, CDCl3): 11.55 (s, 1H), 10.20 (s, 2H), 8.07 (s, 2H).

Computing details top

Data collection: SMART (Siemens 1994-1996); cell refinement: SAINT (Siemens 1994-1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEP view (SHELXTL; Siemens, 1996) of 5-bromo-2-hydroxybenzene-1,3-dicarbaldehyde showing displacement ellipsoids at the 50% probability level.
5-bromo-2-hydroxybenzene-1,3-dicarbaldehyde top
Crystal data top
C8H5BrO3F(000) = 448
Mr = 229.03Dx = 2.000 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.5206 (15) ÅCell parameters from 3595 reflections
b = 3.9367 (8) Åθ = 1.6–26.8°
c = 25.881 (5) ŵ = 5.36 mm1
β = 96.84 (3)°T = 203 K
V = 760.8 (3) Å3Needle, yellow
Z = 40.15 × 0.06 × 0.04 mm
Data collection top
Siemens SMART CCD
diffractometer
1476 independent reflections
Radiation source: fine-focus sealed tube1280 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.108
ω scans, 1271 frames, 0.30°, 10 s, detector distance 5.5 cm, detector angle 23.0°θmax = 26.8°, θmin = 1.6°
Absorption correction: multi-scan
(Blessing, 1995)
h = 79
Tmin = 0.528, Tmax = 0.807k = 44
3595 measured reflectionsl = 3131
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122All H-atom parameters refined
S = 1.15 w = 1/[σ2(Fo2) + (0.0504P)2 + 1.116P]
where P = (Fo2 + 2Fc2)/3
1476 reflections(Δ/σ)max = 0.021
125 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = 0.77 e Å3
Crystal data top
C8H5BrO3V = 760.8 (3) Å3
Mr = 229.03Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.5206 (15) ŵ = 5.36 mm1
b = 3.9367 (8) ÅT = 203 K
c = 25.881 (5) Å0.15 × 0.06 × 0.04 mm
β = 96.84 (3)°
Data collection top
Siemens SMART CCD
diffractometer
1476 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
1280 reflections with I > 2σ(I)
Tmin = 0.528, Tmax = 0.807Rint = 0.108
3595 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.122All H-atom parameters refined
S = 1.15Δρmax = 0.62 e Å3
1476 reflectionsΔρmin = 0.77 e Å3
125 parameters
Special details top

Experimental. H atoms were located in a difference map, and their coordinates were allowed to refine, with Uiso(H) equal to 1.5 Uiso of the corresponding carbon.

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
xyzUiso*/Ueq
Br0.22223 (5)0.23808 (10)0.015353 (16)0.0332 (2)
O40.6948 (4)0.1580 (9)0.20916 (12)0.0318 (7)
H40.627 (9)0.282 (13)0.228 (3)0.040 (6)*
O70.9031 (4)0.4441 (9)0.10756 (14)0.0433 (8)
O80.4140 (4)0.4438 (8)0.24075 (12)0.0352 (7)
C10.3673 (5)0.1103 (10)0.07678 (16)0.0254 (8)
C20.5444 (6)0.2136 (10)0.08367 (18)0.0262 (9)
H20.597 (8)0.342 (13)0.056 (2)0.040 (6)*
C30.6543 (5)0.1263 (11)0.12867 (15)0.0244 (8)
C40.5851 (5)0.0690 (10)0.16694 (14)0.0231 (8)
C50.4035 (5)0.1650 (10)0.15984 (16)0.0238 (8)
C60.2966 (5)0.0769 (10)0.11430 (16)0.0249 (8)
H60.178 (8)0.164 (14)0.112 (2)0.040 (6)*
C70.8420 (6)0.2418 (11)0.13658 (19)0.0302 (10)
H70.909 (8)0.151 (13)0.166 (2)0.040 (6)*
C80.3281 (6)0.3607 (11)0.19971 (16)0.0267 (8)
H80.205 (7)0.432 (13)0.192 (2)0.040 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.0287 (3)0.0403 (3)0.0275 (3)0.00088 (17)0.00899 (19)0.00215 (17)
O40.0237 (14)0.0465 (17)0.0230 (15)0.0047 (14)0.0067 (12)0.0032 (14)
O70.0262 (15)0.054 (2)0.049 (2)0.0078 (15)0.0019 (14)0.0066 (17)
O80.0300 (15)0.0456 (19)0.0296 (16)0.0030 (14)0.0017 (12)0.0026 (14)
C10.0211 (19)0.026 (2)0.027 (2)0.0020 (16)0.0032 (15)0.0027 (17)
C20.0214 (19)0.029 (2)0.029 (2)0.0001 (16)0.0022 (16)0.0035 (17)
C30.0196 (18)0.0301 (19)0.023 (2)0.0011 (16)0.0006 (14)0.0065 (17)
C40.0191 (17)0.029 (2)0.0202 (18)0.0041 (15)0.0034 (14)0.0060 (16)
C50.0232 (19)0.0253 (19)0.023 (2)0.0019 (15)0.0023 (16)0.0049 (16)
C60.0151 (18)0.029 (2)0.029 (2)0.0020 (15)0.0036 (15)0.0046 (17)
C70.0180 (19)0.042 (3)0.031 (2)0.0002 (17)0.0029 (17)0.0015 (19)
C80.0222 (19)0.032 (2)0.025 (2)0.0014 (17)0.0015 (16)0.0050 (18)
Geometric parameters (Å, º) top
Br—C11.886 (4)C3—C41.402 (6)
O4—C41.335 (5)C3—C71.474 (6)
O4—H40.89 (6)C4—C51.408 (5)
O7—C71.221 (6)C5—C61.389 (6)
O8—C81.220 (5)C5—C81.456 (6)
C1—C61.376 (6)C6—H60.95 (6)
C1—C21.384 (6)C7—H70.94 (6)
C2—C31.388 (6)C8—H80.96 (5)
C2—H21.00 (6)
C4—O4—H4105 (4)C6—C5—C4119.9 (4)
C6—C1—C2120.9 (4)C6—C5—C8119.9 (4)
C6—C1—Br120.3 (3)C4—C5—C8120.2 (4)
C2—C1—Br118.8 (3)C1—C6—C5120.0 (4)
C1—C2—C3120.2 (4)C1—C6—H6126 (3)
C1—C2—H2121 (3)C5—C6—H6114 (3)
C3—C2—H2119 (3)O7—C7—C3122.7 (4)
C2—C3—C4119.7 (4)O7—C7—H7123 (3)
C2—C3—C7120.3 (4)C3—C7—H7114 (3)
C4—C3—C7120.0 (4)O8—C8—C5123.3 (4)
O4—C4—C3118.5 (3)O8—C8—H8120 (3)
O4—C4—C5122.1 (4)C5—C8—H8116 (3)
C3—C4—C5119.4 (3)
C6—C1—C2—C30.6 (6)O4—C4—C5—C81.5 (6)
Br—C1—C2—C3179.4 (3)C3—C4—C5—C8178.5 (4)
C1—C2—C3—C40.4 (6)C2—C1—C6—C50.1 (6)
C1—C2—C3—C7178.8 (4)Br—C1—C6—C5178.9 (3)
C2—C3—C4—O4178.1 (4)C4—C5—C6—C11.5 (6)
C7—C3—C4—O42.7 (6)C8—C5—C6—C1179.5 (4)
C2—C3—C4—C51.9 (6)C2—C3—C7—O77.9 (7)
C7—C3—C4—C5177.3 (4)C4—C3—C7—O7171.3 (4)
O4—C4—C5—C6177.6 (4)C6—C5—C8—O8179.3 (4)
C3—C4—C5—C62.5 (6)C4—C5—C8—O81.6 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O80.8911.7912.608 (7)151.47
O4—H4···O4i0.8912.4742.935 (7)112.69
C2—H2···Brii1.0012.9273.921 (5)172.68
C6—H6···O7iii0.9542.5693.495 (9)164.28
C7—H7···O40.9412.3952.779 (8)104.17
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x1, y1, z.

Experimental details

Crystal data
Chemical formulaC8H5BrO3
Mr229.03
Crystal system, space groupMonoclinic, P21/n
Temperature (K)203
a, b, c (Å)7.5206 (15), 3.9367 (8), 25.881 (5)
β (°) 96.84 (3)
V3)760.8 (3)
Z4
Radiation typeMo Kα
µ (mm1)5.36
Crystal size (mm)0.15 × 0.06 × 0.04
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.528, 0.807
No. of measured, independent and
observed [I > 2σ(I)] reflections
3595, 1476, 1280
Rint0.108
(sin θ/λ)max1)0.634
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.122, 1.15
No. of reflections1476
No. of parameters125
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.62, 0.77

Computer programs: SMART (Siemens 1994-1996), SAINT (Siemens 1994-1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O80.8911.7912.608 (7)151.47
O4—H4···O4i0.8912.4742.935 (7)112.69
C2—H2···Brii1.0012.9273.921 (5)172.68
C6—H6···O7iii0.9542.5693.495 (9)164.28
C7—H7···O40.9412.3952.779 (8)104.17
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x1, y1, z.
 

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