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

Jiang, J.-C.; Wang, G.; You, W.; Huang, W.

doi:10.1107/S1600536808020217

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1426

doi:10.1107/S1600536808020217

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

Jue-Chao Jiang,^a Gang Wang,^a Wei You ^b and Wei Huang ^a ^*

^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 , 2006 ); Chu et al. (2005 ); Chu & Huang (2006 ).

Experimental

Crystal data

C₈H₅ClO₃
M_r = 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 ) 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[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
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); 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/S1600536808020217/nc2109sup1.cif

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

checkCIF report

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 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).

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.

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 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).

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

Crystal data top

C₈H₅ClO₃	F(000) = 376
M_r = 184.57	D_x = 1.630 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1370 reflections
a = 7.5554 (15) Å	θ = 2.7–28.1°
b = 3.9144 (8) Å	µ = 0.46 mm⁻¹
c = 25.676 (5) Å	T = 291 K
β = 97.921 (3)°	Block, yellow
V = 752.1 (3) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1353 independent reflections
Radiation source: fine-focus sealed tube	1070 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→8
T_min = 0.913, T_max = 0.930	k = −4→4
3517 measured reflections	l = −30→28

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0457P)²] where P = (F_o² + 2F_c²)/3
1353 reflections	(Δ/σ)_max = 0.001
125 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₅ClO₃	V = 752.1 (3) Å³
M_r = 184.57	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5554 (15) Å	µ = 0.46 mm⁻¹
b = 3.9144 (8) Å	T = 291 K
c = 25.676 (5) Å	0.20 × 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)
T_min = 0.913, T_max = 0.930	R_int = 0.076
3517 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.19 e Å⁻³
1353 reflections	Δρ_min = −0.27 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.4171 (2)	0.4316 (4)	0.33617 (6)	0.0342 (4)
C2	0.5238 (2)	0.6213 (5)	0.37437 (7)	0.0355 (4)
C3	0.4574 (2)	0.7115 (5)	0.42026 (8)	0.0384 (4)
C4	0.2876 (2)	0.6140 (5)	0.42836 (7)	0.0382 (4)
C5	0.1802 (2)	0.4303 (5)	0.39068 (7)	0.0372 (4)
C6	0.2425 (2)	0.3385 (5)	0.34400 (7)	0.0348 (4)
C7	0.7038 (3)	0.7330 (5)	0.36545 (9)	0.0447 (5)
C8	0.1285 (3)	0.1496 (5)	0.30341 (8)	0.0426 (5)
Cl1	0.20868 (7)	0.73166 (14)	0.486064 (19)	0.0550 (2)
H3	0.532 (3)	0.831 (5)	0.4454 (7)	0.047 (5)*
H5	0.064 (3)	0.358 (5)	0.3977 (8)	0.052 (5)*
H7	0.747 (3)	0.653 (5)	0.3360 (8)	0.052 (6)*
H8	0.015 (2)	0.099 (5)	0.3119 (7)	0.044 (5)*
O1	0.48613 (16)	0.3399 (3)	0.29244 (5)	0.0467 (4)
H1	0.4106	0.2351	0.2726	0.070*
O2	0.79414 (18)	0.9339 (4)	0.39307 (6)	0.0606 (4)
O3	0.17345 (17)	0.0628 (4)	0.26168 (5)	0.0544 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0313 (9)	0.0364 (10)	0.0359 (9)	0.0027 (8)	0.0079 (7)	0.0064 (8)
C2	0.0293 (9)	0.0375 (10)	0.0404 (10)	0.0016 (8)	0.0068 (7)	0.0059 (8)
C3	0.0349 (10)	0.0375 (11)	0.0424 (11)	−0.0001 (8)	0.0034 (8)	0.0017 (8)
C4	0.0372 (10)	0.0403 (10)	0.0388 (10)	0.0048 (8)	0.0110 (8)	0.0052 (8)
C5	0.0266 (9)	0.0412 (11)	0.0447 (10)	0.0026 (8)	0.0078 (8)	0.0096 (8)
C6	0.0295 (10)	0.0352 (10)	0.0392 (10)	0.0020 (7)	0.0026 (7)	0.0074 (8)
C7	0.0320 (11)	0.0524 (13)	0.0504 (12)	−0.0027 (9)	0.0083 (9)	−0.0016 (10)
C8	0.0329 (11)	0.0487 (12)	0.0456 (11)	−0.0010 (9)	0.0036 (8)	0.0062 (9)
Cl1	0.0548 (4)	0.0668 (4)	0.0475 (3)	−0.0021 (2)	0.0221 (2)	−0.0052 (2)
O1	0.0400 (7)	0.0626 (9)	0.0393 (7)	−0.0074 (6)	0.0120 (5)	−0.0060 (6)
O2	0.0404 (8)	0.0732 (10)	0.0689 (9)	−0.0158 (8)	0.0099 (7)	−0.0082 (8)
O3	0.0454 (8)	0.0680 (10)	0.0488 (8)	−0.0076 (7)	0.0036 (6)	−0.0092 (7)

Geometric parameters (Å, º) top

C1—O1	1.3500 (19)	C5—C6	1.394 (2)
C1—C2	1.395 (2)	C5—H5	0.96 (2)
C1—C6	1.409 (2)	C6—C8	1.459 (3)
C2—C3	1.388 (2)	C7—O2	1.206 (2)
C2—C7	1.476 (2)	C7—H7	0.92 (2)
C3—C4	1.382 (2)	C8—O3	1.216 (2)
C3—H3	0.926 (19)	C8—H8	0.938 (18)
C4—C5	1.377 (3)	O1—H1	0.8200
C4—Cl1	1.7337 (17)

O1—C1—C2	118.32 (15)	C4—C5—H5	119.1 (12)
O1—C1—C6	121.75 (15)	C6—C5—H5	120.6 (12)
C2—C1—C6	119.93 (15)	C5—C6—C1	119.33 (16)
C3—C2—C1	119.40 (16)	C5—C6—C8	120.57 (16)
C3—C2—C7	120.30 (17)	C1—C6—C8	120.10 (16)
C1—C2—C7	120.27 (16)	O2—C7—C2	124.11 (19)
C4—C3—C2	120.61 (18)	O2—C7—H7	118.0 (13)
C4—C3—H3	121.7 (12)	C2—C7—H7	117.8 (13)
C2—C3—H3	117.7 (12)	O3—C8—C6	124.18 (18)
C5—C4—C3	120.54 (16)	O3—C8—H8	121.5 (11)
C5—C4—Cl1	120.03 (13)	C6—C8—H8	114.3 (11)
C3—C4—Cl1	119.42 (15)	C1—O1—H1	109.5
C4—C5—C6	120.17 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₅ClO₃
M_r	184.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	7.5554 (15), 3.9144 (8), 25.676 (5)
β (°)	97.921 (3)
V (Å³)	752.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.913, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	3517, 1353, 1070
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.091, 0.97
No. of reflections	1353
No. of parameters	125
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.27

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

Selected geometric parameters (Å, º) top

C1—O1	1.3500 (19)	C7—O2	1.206 (2)
C2—C7	1.476 (2)	C8—O3	1.216 (2)
C6—C8	1.459 (3)

O2—C7—C2	124.11 (19)	O3—C8—C6	124.18 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	2.48	2.9581 (19)	118.2
O1—H1···O3	0.82	1.90	2.6204 (18)	146.2

Symmetry code: (i) −x+1, y−1/2, −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

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