organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aState Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, People's Republic of China, and bCollege of Sciences, Nanjing University of Technology, Nanjing, 210009, People's Republic of China
*Correspondence e-mail: whuang@nju.edu.cn

(Received 23 June 2008; accepted 2 July 2008; online 9 July 2008)

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[Huang, W., Gou, S. H., Hu, D. H. & Meng, Q. J. (2000). Synth. Commun. 30, 1555-1561.], 2006[Huang, W., Zhu, H. B. & Gou, S. H. (2006). Coord. Chem. Rev. 250, 414-423.]); Chu et al. (2005[Chu, Z.-L., Huang, W. & Gou, S.-H. (2005). Acta Cryst. E61, o1624-o1626.]); Chu & Huang (2006[Chu, Z.-L. & Huang, W. (2006). Acta Cryst. E62, o675-o677.]).

[Scheme 1]

Experimental

Crystal data
  • C8H5ClO3

  • Mr = 184.57

  • Monoclinic, P 21 /c

  • 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[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.913, Tmax = 0.930

  • 3517 measured reflections

  • 1353 independent reflections

  • 1070 reflections with I > 2σ(I)

  • Rint = 0.076

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O1i 0.82 2.48 2.9581 (19) 118
O1—H1⋯O3 0.82 1.90 2.6204 (18) 146
Symmetry code: (i) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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 ππ 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).

Related literature top

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

Experimental top

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 top

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).

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
[Figure 1] 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.
[Figure 2] Fig. 2. A perspective view of the one-dimensional hydrogen-bonded chain of the title compound.
[Figure 3] 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).
5-Chloro-2-hydroxybenzene-1,3-dicarbaldehyde top
Crystal data top
C8H5ClO3F(000) = 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 = 2.7–28.1°
b = 3.9144 (8) ŵ = 0.46 mm1
c = 25.676 (5) ÅT = 291 K
β = 97.921 (3)°Block, yellow
V = 752.1 (3) Å30.20 × 0.18 × 0.16 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1353 independent reflections
Radiation source: fine-focus sealed tube1070 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.076
ϕ and ω scansθmax = 25.2°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 98
Tmin = 0.913, Tmax = 0.930k = 44
3517 measured reflectionsl = 3028
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 0.97 w = 1/[σ2(Fo2) + (0.0457P)2]
where P = (Fo2 + 2Fc2)/3
1353 reflections(Δ/σ)max = 0.001
125 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C8H5ClO3V = 752.1 (3) Å3
Mr = 184.57Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5554 (15) ŵ = 0.46 mm1
b = 3.9144 (8) ÅT = 291 K
c = 25.676 (5) Å0.20 × 0.18 × 0.16 mm
β = 97.921 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1353 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1070 reflections with I > 2σ(I)
Tmin = 0.913, Tmax = 0.930Rint = 0.076
3517 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.19 e Å3
1353 reflectionsΔρmin = 0.27 e Å3
125 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
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) top
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, º) top
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, º) top
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 code: (i) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC8H5ClO3
Mr184.57
Crystal system, space groupMonoclinic, P21/c
Temperature (K)291
a, b, c (Å)7.5554 (15), 3.9144 (8), 25.676 (5)
β (°) 97.921 (3)
V3)752.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.46
Crystal size (mm)0.20 × 0.18 × 0.16
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.913, 0.930
No. of measured, independent and
observed [I > 2σ(I)] reflections
3517, 1353, 1070
Rint0.076
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.091, 0.97
No. of reflections1353
No. of parameters125
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.27

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

Selected geometric parameters (Å, º) top
C1—O11.3500 (19)C7—O21.206 (2)
C2—C71.476 (2)C8—O31.216 (2)
C6—C81.459 (3)
O2—C7—C2124.11 (19)O3—C8—C6124.18 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1i0.822.482.9581 (19)118.2
O1—H1···O30.821.902.6204 (18)146.2
Symmetry code: (i) x+1, y1/2, z+1/2.
 

Acknowledgements

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.

References

First citationBruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChu, Z.-L. & Huang, W. (2006). Acta Cryst. E62, o675–o677.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationChu, Z.-L., Huang, W. & Gou, S.-H. (2005). Acta Cryst. E61, o1624–o1626.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationHuang, W., Gou, S. H., Hu, D. H. & Meng, Q. J. (2000). Synth. Commun. 30, 1555–1561.  Web of Science CrossRef CAS Google Scholar
First citationHuang, W., Zhu, H. B. & Gou, S. H. (2006). Coord. Chem. Rev. 250, 414–423.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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COMMUNICATIONS
ISSN: 2056-9890
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