Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013630/cv6044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013630/cv6044Isup2.hkl |
CCDC reference: 172221
Key indicators
- Single-crystal X-ray study
- T = 203 K
- Mean (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
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
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).
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.
Fig. 1. ORTEP view (SHELXTL; Siemens, 1996) of 5-bromo-2-hydroxybenzene-1,3-dicarbaldehyde showing displacement ellipsoids at the 50% probability level. |
C8H5BrO3 | F(000) = 448 |
Mr = 229.03 | Dx = 2.000 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5206 (15) Å | Cell parameters from 3595 reflections |
b = 3.9367 (8) Å | θ = 1.6–26.8° |
c = 25.881 (5) Å | µ = 5.36 mm−1 |
β = 96.84 (3)° | T = 203 K |
V = 760.8 (3) Å3 | Needle, yellow |
Z = 4 | 0.15 × 0.06 × 0.04 mm |
Siemens SMART CCD diffractometer | 1476 independent reflections |
Radiation source: fine-focus sealed tube | 1280 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 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 = −7→9 |
Tmin = 0.528, Tmax = 0.807 | k = −4→4 |
3595 measured reflections | l = −31→31 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | All 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 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.77 e Å−3 |
C8H5BrO3 | V = 760.8 (3) Å3 |
Mr = 229.03 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5206 (15) Å | µ = 5.36 mm−1 |
b = 3.9367 (8) Å | T = 203 K |
c = 25.881 (5) Å | 0.15 × 0.06 × 0.04 mm |
β = 96.84 (3)° |
Siemens SMART CCD diffractometer | 1476 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1280 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.807 | Rint = 0.108 |
3595 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.122 | All H-atom parameters refined |
S = 1.15 | Δρmax = 0.62 e Å−3 |
1476 reflections | Δρmin = −0.77 e Å−3 |
125 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br | 0.22223 (5) | 0.23808 (10) | 0.015353 (16) | 0.0332 (2) | |
O4 | 0.6948 (4) | −0.1580 (9) | 0.20916 (12) | 0.0318 (7) | |
H4 | 0.627 (9) | −0.282 (13) | 0.228 (3) | 0.040 (6)* | |
O7 | 0.9031 (4) | 0.4441 (9) | 0.10756 (14) | 0.0433 (8) | |
O8 | 0.4140 (4) | −0.4438 (8) | 0.24075 (12) | 0.0352 (7) | |
C1 | 0.3673 (5) | 0.1103 (10) | 0.07678 (16) | 0.0254 (8) | |
C2 | 0.5444 (6) | 0.2136 (10) | 0.08367 (18) | 0.0262 (9) | |
H2 | 0.597 (8) | 0.342 (13) | 0.056 (2) | 0.040 (6)* | |
C3 | 0.6543 (5) | 0.1263 (11) | 0.12867 (15) | 0.0244 (8) | |
C4 | 0.5851 (5) | −0.0690 (10) | 0.16694 (14) | 0.0231 (8) | |
C5 | 0.4035 (5) | −0.1650 (10) | 0.15984 (16) | 0.0238 (8) | |
C6 | 0.2966 (5) | −0.0769 (10) | 0.11430 (16) | 0.0249 (8) | |
H6 | 0.178 (8) | −0.164 (14) | 0.112 (2) | 0.040 (6)* | |
C7 | 0.8420 (6) | 0.2418 (11) | 0.13658 (19) | 0.0302 (10) | |
H7 | 0.909 (8) | 0.151 (13) | 0.166 (2) | 0.040 (6)* | |
C8 | 0.3281 (6) | −0.3607 (11) | 0.19971 (16) | 0.0267 (8) | |
H8 | 0.205 (7) | −0.432 (13) | 0.192 (2) | 0.040 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0287 (3) | 0.0403 (3) | 0.0275 (3) | −0.00088 (17) | −0.00899 (19) | 0.00215 (17) |
O4 | 0.0237 (14) | 0.0465 (17) | 0.0230 (15) | −0.0047 (14) | −0.0067 (12) | 0.0032 (14) |
O7 | 0.0262 (15) | 0.054 (2) | 0.049 (2) | −0.0078 (15) | 0.0019 (14) | 0.0066 (17) |
O8 | 0.0300 (15) | 0.0456 (19) | 0.0296 (16) | −0.0030 (14) | 0.0017 (12) | 0.0026 (14) |
C1 | 0.0211 (19) | 0.026 (2) | 0.027 (2) | 0.0020 (16) | −0.0032 (15) | −0.0027 (17) |
C2 | 0.0214 (19) | 0.029 (2) | 0.029 (2) | −0.0001 (16) | 0.0022 (16) | −0.0035 (17) |
C3 | 0.0196 (18) | 0.0301 (19) | 0.023 (2) | −0.0011 (16) | −0.0006 (14) | −0.0065 (17) |
C4 | 0.0191 (17) | 0.029 (2) | 0.0202 (18) | 0.0041 (15) | −0.0034 (14) | −0.0060 (16) |
C5 | 0.0232 (19) | 0.0253 (19) | 0.023 (2) | −0.0019 (15) | 0.0023 (16) | −0.0049 (16) |
C6 | 0.0151 (18) | 0.029 (2) | 0.029 (2) | 0.0020 (15) | −0.0036 (15) | −0.0046 (17) |
C7 | 0.0180 (19) | 0.042 (3) | 0.031 (2) | 0.0002 (17) | 0.0029 (17) | 0.0015 (19) |
C8 | 0.0222 (19) | 0.032 (2) | 0.025 (2) | −0.0014 (17) | 0.0015 (16) | −0.0050 (18) |
Br—C1 | 1.886 (4) | C3—C4 | 1.402 (6) |
O4—C4 | 1.335 (5) | C3—C7 | 1.474 (6) |
O4—H4 | 0.89 (6) | C4—C5 | 1.408 (5) |
O7—C7 | 1.221 (6) | C5—C6 | 1.389 (6) |
O8—C8 | 1.220 (5) | C5—C8 | 1.456 (6) |
C1—C6 | 1.376 (6) | C6—H6 | 0.95 (6) |
C1—C2 | 1.384 (6) | C7—H7 | 0.94 (6) |
C2—C3 | 1.388 (6) | C8—H8 | 0.96 (5) |
C2—H2 | 1.00 (6) | ||
C4—O4—H4 | 105 (4) | C6—C5—C4 | 119.9 (4) |
C6—C1—C2 | 120.9 (4) | C6—C5—C8 | 119.9 (4) |
C6—C1—Br | 120.3 (3) | C4—C5—C8 | 120.2 (4) |
C2—C1—Br | 118.8 (3) | C1—C6—C5 | 120.0 (4) |
C1—C2—C3 | 120.2 (4) | C1—C6—H6 | 126 (3) |
C1—C2—H2 | 121 (3) | C5—C6—H6 | 114 (3) |
C3—C2—H2 | 119 (3) | O7—C7—C3 | 122.7 (4) |
C2—C3—C4 | 119.7 (4) | O7—C7—H7 | 123 (3) |
C2—C3—C7 | 120.3 (4) | C3—C7—H7 | 114 (3) |
C4—C3—C7 | 120.0 (4) | O8—C8—C5 | 123.3 (4) |
O4—C4—C3 | 118.5 (3) | O8—C8—H8 | 120 (3) |
O4—C4—C5 | 122.1 (4) | C5—C8—H8 | 116 (3) |
C3—C4—C5 | 119.4 (3) | ||
C6—C1—C2—C3 | 0.6 (6) | O4—C4—C5—C8 | 1.5 (6) |
Br—C1—C2—C3 | 179.4 (3) | C3—C4—C5—C8 | −178.5 (4) |
C1—C2—C3—C4 | 0.4 (6) | C2—C1—C6—C5 | −0.1 (6) |
C1—C2—C3—C7 | −178.8 (4) | Br—C1—C6—C5 | −178.9 (3) |
C2—C3—C4—O4 | 178.1 (4) | C4—C5—C6—C1 | −1.5 (6) |
C7—C3—C4—O4 | −2.7 (6) | C8—C5—C6—C1 | 179.5 (4) |
C2—C3—C4—C5 | −1.9 (6) | C2—C3—C7—O7 | 7.9 (7) |
C7—C3—C4—C5 | 177.3 (4) | C4—C3—C7—O7 | −171.3 (4) |
O4—C4—C5—C6 | −177.6 (4) | C6—C5—C8—O8 | −179.3 (4) |
C3—C4—C5—C6 | 2.5 (6) | C4—C5—C8—O8 | 1.6 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O8 | 0.891 | 1.791 | 2.608 (7) | 151.47 |
O4—H4···O4i | 0.891 | 2.474 | 2.935 (7) | 112.69 |
C2—H2···Brii | 1.001 | 2.927 | 3.921 (5) | 172.68 |
C6—H6···O7iii | 0.954 | 2.569 | 3.495 (9) | 164.28 |
C7—H7···O4 | 0.941 | 2.395 | 2.779 (8) | 104.17 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C8H5BrO3 |
Mr | 229.03 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 203 |
a, b, c (Å) | 7.5206 (15), 3.9367 (8), 25.881 (5) |
β (°) | 96.84 (3) |
V (Å3) | 760.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.36 |
Crystal size (mm) | 0.15 × 0.06 × 0.04 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.528, 0.807 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3595, 1476, 1280 |
Rint | 0.108 |
(sin θ/λ)max (Å−1) | 0.634 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.122, 1.15 |
No. of reflections | 1476 |
No. of parameters | 125 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O8 | 0.891 | 1.791 | 2.608 (7) | 151.47 |
O4—H4···O4i | 0.891 | 2.474 | 2.935 (7) | 112.69 |
C2—H2···Brii | 1.001 | 2.927 | 3.921 (5) | 172.68 |
C6—H6···O7iii | 0.954 | 2.569 | 3.495 (9) | 164.28 |
C7—H7···O4 | 0.941 | 2.395 | 2.779 (8) | 104.17 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x−1, y−1, z. |
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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).