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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1426.
Published online 2008 July 9. doi:  10.1107/S1600536808020217
PMCID: PMC2962059

5-Chloro-2-hydroxy­benzene-1,3-dicarb­aldehyde

Abstract

In the crystal structure of the title compound, C8H5ClO3, both formyl groups are in the plane of the chloro­phenyl unit and the mol­ecule is stabilized by intra­molecular O—H(...)O hydrogen bonding. The mol­ecules are connected via inter­molecular O—H(...)O hydrogen bonding into chains and are stacked into columns with a centroid–centroid distance between adjacent aromatic rings of 3.914 (2) Å.

Related literature

For related compounds, see: Huang et al. (2000 [triangle], 2006 [triangle]); Chu et al. (2005 [triangle]); Chu & Huang (2006 [triangle]).

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Object name is e-64-o1426-scheme1.jpg

Experimental

Crystal data

  • C8H5ClO3
  • M r = 184.57
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1426-efi1.jpg
  • a = 7.5554 (15) Å
  • b = 3.9144 (8) Å
  • c = 25.676 (5) Å
  • β = 97.921 (3)°
  • V = 752.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.46 mm−1
  • T = 291 (2) K
  • 0.20 × 0.18 × 0.16 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.913, T max = 0.930
  • 3517 measured reflections
  • 1353 independent reflections
  • 1070 reflections with I > 2σ(I)
  • R int = 0.076

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.091
  • S = 0.97
  • 1353 reflections
  • 125 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.27 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808020217/nc2109sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020217/nc2109Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

WH acknowledges the Major State Basic Research Development Programs (grant Nos. 2006CB806104 and 2007CB925101) and the National Natural Science Foundation of China (grant No. 20301009) for financial aid.

supplementary crystallographic information

Comment

Hydroxyisophthalaldehyde and its derivatives are an important class of intermediates used in synthesizing macrocyclic compounds. In recent years, a continuing attention has been drawn to them and their metal complexes (Huang et al., 2006). In this paper, we report the X-ray single-crystal structure of 2,6-diformyl-4-chlorophenol prepared from 4-chloro-2,6-bis(hydroxymethyl)phenol.

The molecule of the title compound is essentially planar and all structural parameters (Fig. 1) are in good agreement with those found in similar compounds (Chu et al., 2005; Chu & Huang, 2006). There is one weak intramolecular O-H···O hydrogen bond between the hydroxyl group at O1 and the carbonyl group O3.

In the crystal structure of the title compound the molecules are connected into chains by intermolecular O-H···O hydrogen bonding (Fig. 2 and Table 1). The molecules are stacked into columns in the direction of the crystallographic a-axis in order that π–π stacking interactions are maximized. The dihedral angle between two adjacent rings amount to 63.5 (2)° and the centroid-centroid separation is 3.914 (2) Å (Fig. 3).

Experimental

4-Chloro-2,6-diformylphenol was prepared by an improved oxidation method using activated manganese (IV) dioxide (Huang et al., 2000) from 4-chloro-2,6-bis(hydroxymethyl)phenol (Chu et al., 2005). Single crystals suitable for X-ray diffraction measurement were grown from a chloroform solution by slow evaporation of the solvent at room temperature.

Refinement

The C-H H atoms were located in difference map and were refined with varying coordinates isotropic. The O-H H atom was placed with idealized geometry allowed to rotata but not to tip O—H = 0.82 Å) and was refined using a riding model with Uiso(H) = 1.5Ueq(O).

Figures

Fig. 1.
An ORTEP drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and intramolecular hydrogen bonds is shown as dashed lines.
Fig. 2.
A perspective view of the one-dimensional hydrogen-bonded chain of the title compound.
Fig. 3.
Crystal structure of the title compound with view along the a-axis (intermolecular O-H···O hydrogen bonding is shown as dashed lines).

Crystal data

C8H5ClO3F000 = 376
Mr = 184.57Dx = 1.630 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1370 reflections
a = 7.5554 (15) Åθ = 2.7–28.1º
b = 3.9144 (8) ŵ = 0.46 mm1
c = 25.676 (5) ÅT = 291 (2) K
β = 97.921 (3)ºBlock, yellow
V = 752.1 (3) Å30.20 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1353 independent reflections
Radiation source: fine-focus sealed tube1070 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.076
T = 291(2) Kθmax = 25.2º
[var phi] and ω scansθmin = 2.7º
Absorption correction: multi-scan(SADABS; Bruker, 2000)h = −9→8
Tmin = 0.913, Tmax = 0.930k = −4→4
3517 measured reflectionsl = −30→28

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091  w = 1/[σ2(Fo2) + (0.0457P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max = 0.001
1353 reflectionsΔρmax = 0.19 e Å3
125 parametersΔρmin = −0.27 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
C10.4171 (2)0.4316 (4)0.33617 (6)0.0342 (4)
C20.5238 (2)0.6213 (5)0.37437 (7)0.0355 (4)
C30.4574 (2)0.7115 (5)0.42026 (8)0.0384 (4)
C40.2876 (2)0.6140 (5)0.42836 (7)0.0382 (4)
C50.1802 (2)0.4303 (5)0.39068 (7)0.0372 (4)
C60.2425 (2)0.3385 (5)0.34400 (7)0.0348 (4)
C70.7038 (3)0.7330 (5)0.36545 (9)0.0447 (5)
C80.1285 (3)0.1496 (5)0.30341 (8)0.0426 (5)
Cl10.20868 (7)0.73166 (14)0.486064 (19)0.0550 (2)
H30.532 (3)0.831 (5)0.4454 (7)0.047 (5)*
H50.064 (3)0.358 (5)0.3977 (8)0.052 (5)*
H70.747 (3)0.653 (5)0.3360 (8)0.052 (6)*
H80.015 (2)0.099 (5)0.3119 (7)0.044 (5)*
O10.48613 (16)0.3399 (3)0.29244 (5)0.0467 (4)
H10.41060.23510.27260.070*
O20.79414 (18)0.9339 (4)0.39307 (6)0.0606 (4)
O30.17345 (17)0.0628 (4)0.26168 (5)0.0544 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0313 (9)0.0364 (10)0.0359 (9)0.0027 (8)0.0079 (7)0.0064 (8)
C20.0293 (9)0.0375 (10)0.0404 (10)0.0016 (8)0.0068 (7)0.0059 (8)
C30.0349 (10)0.0375 (11)0.0424 (11)−0.0001 (8)0.0034 (8)0.0017 (8)
C40.0372 (10)0.0403 (10)0.0388 (10)0.0048 (8)0.0110 (8)0.0052 (8)
C50.0266 (9)0.0412 (11)0.0447 (10)0.0026 (8)0.0078 (8)0.0096 (8)
C60.0295 (10)0.0352 (10)0.0392 (10)0.0020 (7)0.0026 (7)0.0074 (8)
C70.0320 (11)0.0524 (13)0.0504 (12)−0.0027 (9)0.0083 (9)−0.0016 (10)
C80.0329 (11)0.0487 (12)0.0456 (11)−0.0010 (9)0.0036 (8)0.0062 (9)
Cl10.0548 (4)0.0668 (4)0.0475 (3)−0.0021 (2)0.0221 (2)−0.0052 (2)
O10.0400 (7)0.0626 (9)0.0393 (7)−0.0074 (6)0.0120 (5)−0.0060 (6)
O20.0404 (8)0.0732 (10)0.0689 (9)−0.0158 (8)0.0099 (7)−0.0082 (8)
O30.0454 (8)0.0680 (10)0.0488 (8)−0.0076 (7)0.0036 (6)−0.0092 (7)

Geometric parameters (Å, °)

C1—O11.3500 (19)C5—C61.394 (2)
C1—C21.395 (2)C5—H50.96 (2)
C1—C61.409 (2)C6—C81.459 (3)
C2—C31.388 (2)C7—O21.206 (2)
C2—C71.476 (2)C7—H70.92 (2)
C3—C41.382 (2)C8—O31.216 (2)
C3—H30.926 (19)C8—H80.938 (18)
C4—C51.377 (3)O1—H10.8200
C4—Cl11.7337 (17)
O1—C1—C2118.32 (15)C4—C5—H5119.1 (12)
O1—C1—C6121.75 (15)C6—C5—H5120.6 (12)
C2—C1—C6119.93 (15)C5—C6—C1119.33 (16)
C3—C2—C1119.40 (16)C5—C6—C8120.57 (16)
C3—C2—C7120.30 (17)C1—C6—C8120.10 (16)
C1—C2—C7120.27 (16)O2—C7—C2124.11 (19)
C4—C3—C2120.61 (18)O2—C7—H7118.0 (13)
C4—C3—H3121.7 (12)C2—C7—H7117.8 (13)
C2—C3—H3117.7 (12)O3—C8—C6124.18 (18)
C5—C4—C3120.54 (16)O3—C8—H8121.5 (11)
C5—C4—Cl1120.03 (13)C6—C8—H8114.3 (11)
C3—C4—Cl1119.42 (15)C1—O1—H1109.5
C4—C5—C6120.17 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O1i0.822.482.9581 (19)118
O1—H1···O30.821.902.6204 (18)146

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2109).

References

  • Bruker (2000). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chu, Z.-L. & Huang, W. (2006). Acta Cryst. E62, o675–o677.
  • Chu, Z.-L., Huang, W. & Gou, S.-H. (2005). Acta Cryst. E61, o1624–o1626.
  • Huang, W., Gou, S. H., Hu, D. H. & Meng, Q. J. (2000). Synth. Commun.30, 1555–1561.
  • Huang, W., Zhu, H. B. & Gou, S. H. (2006). Coord. Chem. Rev.250, 414–423.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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