3,6-Dichloro­catechol

Xie, A.-L.; Ding, T.-J.; Cao, X.-P.

doi:10.1107/S1600536808025014

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1746

doi:10.1107/S1600536808025014

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3,6-Dichlorocatechol

An-Le Xie,^a Tong-Jian Ding ^a and Xiao-Ping Cao ^a ^*

^aState Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, People's Republic of China
^*Correspondence e-mail: caoxplzu@163.com

(Received 24 April 2008; accepted 4 August 2008; online 13 August 2008)

The title compound, C₆H₄Cl₂O₂, exhibits a two-dimensional supramolecular hydrogen-bonded network and forms a three-dimensional network supramolecular structure via hydrogen bonds and π–π stacking of benzene rings. The π–π interactions are between the benzene rings of centrosymmetrically related molecules, with centroid–centroid distances of 3.7676 (13) and 3.7107 (13) Å.

Related literature

For related literature, see: Haigler et al. (1988 ); Kirsh & Stan (1994 ); Nishizawa & Satoh (1975a ,b ); Sander et al. (1991 ); Schraa et al. (1986 ); Spiess et al. (1995 ); Spain et al. (1989 ).

Experimental

Crystal data

C₆H₄Cl₂O₂
M_r = 178.99
Monoclinic, P 2₁ /c
a = 7.4411 (7) Å
b = 10.1283 (10) Å
c = 10.6448 (8) Å
β = 119.903 (5)°
V = 695.45 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 296 K
0.36 × 0.17 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.748, T_max = 0.882
3531 measured reflections
1243 independent reflections
1117 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.118
S = 1.01
1243 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	2.19	2.6391 (17)	115
O1—H1⋯Cl1ⁱ	0.82	2.76	3.3980 (16)	137
O2—H2⋯Cl2	0.82	2.61	3.0597 (13)	116
O2—H2⋯O1ⁱⁱ	0.82	2.13	2.8969 (19)	155
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025014/bq2078sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025014/bq2078Isup2.hkl

checkCIF report

Comment top

The compound 3,6-dichlorocatechol, (I), was a common metabolite in the microbial aerobic degradation of 1,4-dichlorobenzene. Because 1,4-dichlorobenzene was too stable to be degraded by photochemistry, biodegradation of this compound was an only way that it was eliminated from enviroment. 3,6-Dichlorocatechol has been reported to be an important intermediate in this process (Haigler et al., 1988; Schraa et al., 1986; Spain et al., 1989; Sander et al., 1991; Spiess et al., 1995). So the title compound (I) could be used to optimize the biodegradation process of 1,4-dichlorobenzene (Kirsh et al., 1994). It would be of great important significance in the protection of our surrounding and public health. Herein, we report the synthesis and structure of this compound, namely 3,6-dichlorocatechol. As shown in Fig.1, there are two hydroxyl groups in the phenyl ring. In the formation of these hydrogen bonds, one acts as donor, the other as acceptor. A two-dimensional supramolecular network was formed by O—H···Cl and O—H···O intermolecular hydrogen bonds (Table 1) [Symmetry codes (i): -x+2, y-1/2, -z+3/2; (ii): x, -y+3/2, z-1/2], and there are also weak π-π interactions between the centrosymmetrically related phenyl rings at (x, y, z) and (-x, -y, -z+1), (-x+1, -y, -z+1) with a centroid-to-centroid distance of 3.7676 (13)Å and 3.7107 (13)Å, respectively (Fig. 2).

Related literature top

For related literature, see: Haigler et al. (1988); Kirsh & Stan (1994); Nishizawa & Satoh (1975a,b); Sander et al. (1991); Schraa et al. (1986); Spiess et al. (1995); Spain et al. (1989).

Experimental top

3,6,6-Tricholor-2-hydroxycyclohex-2-en-1-one (26 g, 0.12 mol) was treated with Li₂CO₃ (13.4 g, 0.18 mol) in DMF to give the title compound (I). (18.4 g) in 86% yield (Nishizawa & Satoh, 1975a,b). m. p. 108-109°C; ¹H NMR (CDCl₃, 300 MHz) δ: 5.79 (s, 2H), 6.86 (d, J = 2.4 Hz, 2H); ¹³ C NMR (CDCl₃, 75 MHz) δ: 118.7, 120.8, 140.6; MS (ESI) m/z (%): 178 (M+, 95), 180 (49), 182 (8).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The three-dimensional structure by molecular packing, showing the intermolecular hydrogen bonds as yellow dashed lines [Symmetry codes: (i) -x+2, y-1/2, -z+3/2; (ii) x, -y+3/2, z-1/2], and π-π interactions as black dashed lines.

3,6-dichlorobenzene-1,2-diol top

Crystal data top

C₆H₄Cl₂O₂	F(000) = 360
M_r = 178.99	D_x = 1.710 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2193 reflections
a = 7.4411 (7) Å	θ = 2.9–26.4°
b = 10.1283 (10) Å	µ = 0.86 mm⁻¹
c = 10.6448 (8) Å	T = 296 K
β = 119.903 (5)°	Block, colorless
V = 695.45 (11) Å³	0.36 × 0.17 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1243 independent reflections
Radiation source: fine-focus sealed tube	1117 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 25.2°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −8→8
T_min = 0.748, T_max = 0.882	k = −9→12
3531 measured reflections	l = −12→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.01P)²] where P = (F_o² + 2F_c²)/3
1243 reflections	(Δ/σ)_max = 0.001
93 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₆H₄Cl₂O₂	V = 695.45 (11) Å³
M_r = 178.99	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4411 (7) Å	µ = 0.86 mm⁻¹
b = 10.1283 (10) Å	T = 296 K
c = 10.6448 (8) Å	0.36 × 0.17 × 0.15 mm
β = 119.903 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1243 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1117 reflections with I > 2σ(I)
T_min = 0.748, T_max = 0.882	R_int = 0.017
3531 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.01	Δρ_max = 0.18 e Å⁻³
1243 reflections	Δρ_min = −0.34 e Å⁻³
93 parameters

Special details top

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
Cl1	0.84969 (7)	1.04043 (6)	0.81747 (4)	0.0483 (3)
Cl2	0.64593 (7)	0.99288 (7)	0.17713 (4)	0.0529 (3)
O1	0.8451 (2)	0.79625 (12)	0.66807 (12)	0.0487 (4)
H1	0.8578	0.7331	0.6249	0.073*
O2	0.7560 (2)	0.76889 (12)	0.39645 (12)	0.0490 (4)
H2	0.7570	0.7708	0.3198	0.074*
C1	0.7904 (3)	1.02895 (16)	0.63843 (18)	0.0344 (4)
C2	0.7954 (2)	0.90633 (16)	0.58289 (15)	0.0335 (4)
C3	0.7515 (2)	0.89485 (16)	0.44037 (17)	0.0330 (4)
C4	0.7012 (3)	1.00694 (18)	0.35485 (17)	0.0356 (4)
C5	0.6955 (3)	1.13066 (18)	0.41095 (17)	0.0433 (4)
H5	0.6619	1.2056	0.3530	0.052*
C6	0.7397 (3)	1.14090 (18)	0.55181 (19)	0.0415 (4)
H6	0.7359	1.2230	0.5896	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0647 (4)	0.0507 (4)	0.0356 (4)	−0.00327 (18)	0.0296 (3)	−0.00797 (16)
Cl2	0.0633 (4)	0.0666 (5)	0.0307 (4)	0.0071 (2)	0.0248 (3)	0.00907 (18)
O1	0.0832 (10)	0.0343 (7)	0.0401 (7)	0.0122 (6)	0.0393 (7)	0.0089 (5)
O2	0.0835 (10)	0.0351 (7)	0.0414 (7)	−0.0021 (6)	0.0409 (7)	−0.0039 (5)
C1	0.0382 (9)	0.0370 (9)	0.0307 (8)	−0.0029 (6)	0.0192 (7)	−0.0042 (6)
C2	0.0394 (8)	0.0323 (9)	0.0317 (8)	0.0010 (7)	0.0199 (7)	0.0053 (6)
C3	0.0373 (8)	0.0334 (9)	0.0298 (7)	−0.0025 (6)	0.0177 (6)	−0.0020 (6)
C4	0.0360 (9)	0.0445 (10)	0.0276 (8)	−0.0007 (7)	0.0169 (7)	0.0042 (7)
C5	0.0488 (10)	0.0354 (9)	0.0450 (9)	0.0037 (7)	0.0230 (8)	0.0100 (7)
C6	0.0508 (10)	0.0309 (9)	0.0429 (8)	0.0009 (7)	0.0234 (7)	−0.0003 (7)

Geometric parameters (Å, º) top

O1—H1	0.8200	C3—O2	1.365 (2)
O2—H2	0.8200	C3—C4	1.385 (2)
C1—C2	1.384 (2)	C4—C5	1.398 (2)
C1—C6	1.390 (2)	C4—Cl2	1.7299 (16)
C1—Cl1	1.7326 (17)	C5—C6	1.369 (3)
C2—O1	1.3666 (18)	C5—H5	0.9300
C2—C3	1.388 (2)	C6—H6	0.9300

O1—C2—C1	120.31 (13)	C3—C4—C5	120.65 (15)
O1—C2—C3	119.68 (14)	C3—C4—Cl2	119.36 (13)
O2—C3—C4	125.85 (14)	C4—C3—C2	119.27 (15)
O2—C3—C2	114.84 (14)	C4—C5—H5	120.2
C1—C2—C3	120.02 (14)	C5—C4—Cl2	119.98 (13)
C1—C6—H6	119.9	C5—C6—C1	120.16 (16)
C2—O1—H1	109.5	C5—C6—H6	119.9
C2—C1—C6	120.32 (15)	C6—C5—C4	119.59 (15)
C2—C1—Cl1	118.94 (12)	C6—C1—Cl1	120.75 (13)
C3—O2—H2	109.5	C6—C5—H5	120.2

Cl1—C1—C2—O1	0.4 (2)	C1—C2—C3—C4	−0.5 (2)
Cl1—C1—C2—C3	−179.06 (12)	C2—C1—C6—C5	−0.3 (3)
Cl1—C1—C6—C5	179.23 (13)	C2—C3—C4—C5	0.3 (2)
Cl2—C4—C5—C6	−179.92 (13)	C2—C3—C4—Cl2	−179.90 (12)
O1—C2—C3—O2	2.1 (2)	C3—C4—C5—C6	−0.1 (3)
O1—C2—C3—C4	179.98 (15)	C4—C5—C6—C1	0.2 (3)
O2—C3—C4—C5	177.97 (16)	C6—C1—C2—O1	−179.97 (15)
O2—C3—C4—Cl2	−2.3 (2)	C6—C1—C2—C3	0.5 (2)
C1—C2—C3—O2	−178.41 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.19	2.6391 (17)	115
O1—H1···Cl1ⁱ	0.82	2.76	3.3980 (16)	137
O2—H2···Cl2	0.82	2.61	3.0597 (13)	116
O2—H2···O1ⁱⁱ	0.82	2.13	2.8969 (19)	155

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₄Cl₂O₂
M_r	178.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.4411 (7), 10.1283 (10), 10.6448 (8)
β (°)	119.903 (5)
V (Å³)	695.45 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.36 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.748, 0.882
No. of measured, independent and observed [I > 2σ(I)] reflections	3531, 1243, 1117
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.118, 1.01
No. of reflections	1243
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.34

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.19	2.6391 (17)	115
O1—H1···Cl1ⁱ	0.82	2.76	3.3980 (16)	137
O2—H2···Cl2	0.82	2.61	3.0597 (13)	116
O2—H2···O1ⁱⁱ	0.82	2.13	2.8969 (19)	155

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x, −y+3/2, z−1/2.

Acknowledgements

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (20621091). The authors are also grateful to Professor Yu Tang, Lanzhou University, for her helpful guidance in the preparation of the manuscript.

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