2,3-Dichloro­benzene-1,4-diol

Ahn, P.D.; Bishop, R.; Craig, D.C.; Scudder, M.L.

doi:10.1107/S1600536809014408

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1103

doi:10.1107/S1600536809014408

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2,3-Dichlorobenzene-1,4-diol

Paul D. Ahn,^a Roger Bishop,^a Donald C. Craig ^a and Marcia L. Scudder ^a ^*

^aSchool of Chemistry, University of New South Wales, Sydney 2052, Australia
^*Correspondence e-mail: m.scudder@unsw.edu.au

(Received 3 March 2009; accepted 17 April 2009; online 25 April 2009)

The achiral title compound, C₆H₄Cl₂O₂, crystallizes with O—H⋯O hydrogen bonding linking molecules into layers. Between layers there are chains of Cl⋯Cl⋯Cl interactions with alternating distances of 3.274 (2) and 3.742 (2) Å. Augmenting this arrangement there are also C—H⋯Cl (2.97 and 3.17 Å) and Cl⋯π (shortest distances 3.40 and 3.54 Å) interactions.

Related literature

For the structures of related dichloronaphthalenediols, see: Ahn et al. (1995 , 1996 ). For the preparation of the title compound, see: Beddoes et al. (1981 ).

Experimental

Crystal data

C₆H₄Cl₂O₂
M_r = 179.0
Monoclinic, P 2₁ /c
a = 4.831 (1) Å
b = 11.347 (2) Å
c = 12.962 (3) Å
β = 105.94 (1)°
V = 683.2 (2) Å³
Z = 4
Cu Kα radiation
μ = 8.02 mm⁻¹
T = 294 K
0.15 × 0.15 × 0.06 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ) T_min = 0.33, T_max = 0.63
1449 measured reflections
1290 independent reflections
1187 reflections with I > 2σ(I)
R_int = 0.041
1 standard reflections frequency: 30 min intensity decay: 21%

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.050
S = 1.87
1290 reflections
92 parameters
H-atom parameters not refined
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2ⁱ	1.00	1.84	2.794 (2)	158
O2—H1O2⋯O1ⁱⁱ	1.00	1.78	2.778 (2)	172
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Manual (Schagen et al., 1989 ); cell refinement: CAD-4 Manual; data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: RAELS (Rae, 2000 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and CrystalMaker (CrystalMaker Software, 2005 ); software used to prepare material for publication: local programs.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014408/bv2117sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014408/bv2117Isup2.hkl

checkCIF report

Comment top

Crystal structures of related dichloronaphthalenediols have been previously reported by us (Ahn et al., 1995, 1996). In the title compound (Fig 1), each molecule participates in four hydrogen bonds, two as donor and two as acceptor, creating a layer structure in the ac plane with O1-H1O1···O2-H1O2···O1-H1O1··· chains parallel to a (Fig 2, Table 1). Aromatic offset face-face stacking at a distance of 3.5 Å takes place within the layer. Chains of Cl1···Cl1···Cl1 interactions (alternating distances 3.274 (2) and 3.742 (2) Å) which also run parallel to a link the layers into a three-dimensional array. In addition there are C5H···Cl2 and C6H···Cl2 (2.97 and 3.17 Å) and Cl2···π interactions (shortest distances 3.40 and 3.54 Å).

Related literature top

For related literature, see: Ahn et al. (1995, 1996); Beddoes et al., (1981).

Experimental top

2,3-Dichlorobenzene-1,4-diol was prepared as described (Beddoes et al., 1981). ¹H NMR (300 MHz, d₆-DMSO) δ 6.79 (s, 2H), 9.71 (s, 2H, –OH); ¹³C NMR (75 MHz, d₆-DMSO) δ 115.1 (CH), 119.2 (C), 147.1 (C). X-ray quality solvent-free crystals were obtained from benzene solution.

Computing details top

Data collection: CAD-4 Manual (Schagen et al., 1989); cell refinement: CAD-4 Manual (Schagen et al., 1989); data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: RAELS (Rae, 2000); molecular graphics: ORTEP-3 (Farrugia, 1997) and CrystalMaker (CrystalMaker Software, 2005); software used to prepare material for publication: local programs.

Figures top

	Fig. 1. A molecule of the title compound, showing atom labelling. Thermal ellipsoids are drawn at the 50% level.
	Fig. 2. A hydrogen bonded layer. Each molecule participates in two donor and two acceptor hydrogen bonds which are represented as dashed lines.

2,3-Dichlorobenzene-1,4-diol top

Crystal data top

C₆H₄Cl₂O₂	F(000) = 360.0
M_r = 179.0	D_x = 1.74 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 4.831 (1) Å	Cell parameters from 10 reflections
b = 11.347 (2) Å	θ = 25–30°
c = 12.962 (3) Å	µ = 8.02 mm⁻¹
β = 105.94 (1)°	T = 294 K
V = 683.2 (2) Å³	Tabular, colourless
Z = 4	0.15 × 0.15 × 0.06 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.041
ω–2θ scans	θ_max = 70°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −5→0
T_min = 0.33, T_max = 0.63	k = −13→0
1449 measured reflections	l = −15→15
1290 independent reflections	1 standard reflections every 30 min
1187 reflections with I > 2σ(I)	intensity decay: 21%

Refinement top

Refinement on F	0 restraints
R[F² > 2σ(F²)] = 0.034	H-atom parameters not refined
wR(F²) = 0.050	w = 1/[σ²(F) + 0.0004F²]
S = 1.87	(Δ/σ)_max = 0.008
1290 reflections	Δρ_max = 0.42 e Å⁻³
92 parameters	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₆H₄Cl₂O₂	V = 683.2 (2) Å³
M_r = 179.0	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 4.831 (1) Å	µ = 8.02 mm⁻¹
b = 11.347 (2) Å	T = 294 K
c = 12.962 (3) Å	0.15 × 0.15 × 0.06 mm
β = 105.94 (1)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1187 reflections with I > 2σ(I)
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	R_int = 0.041
T_min = 0.33, T_max = 0.63	1 standard reflections every 30 min
1449 measured reflections	intensity decay: 21%
1290 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.050	H-atom parameters not refined
S = 1.87	Δρ_max = 0.42 e Å⁻³
1290 reflections	Δρ_min = −0.31 e Å⁻³
92 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.78228 (10)	0.11149 (4)	0.49607 (4)	0.0444 (2)
Cl2	0.54566 (11)	0.00422 (4)	0.26478 (4)	0.0439 (2)
O1	0.4715 (3)	0.3170 (1)	0.5364 (1)	0.0463 (4)
O2	0.0408 (3)	0.1224 (1)	0.1331 (1)	0.0404 (4)
C1	0.3548 (4)	0.2698 (2)	0.4364 (2)	0.0340 (4)
C2	0.4868 (4)	0.1726 (2)	0.4063 (1)	0.0328 (4)
C3	0.3797 (4)	0.1238 (2)	0.3049 (2)	0.0319 (4)
C4	0.1366 (4)	0.1719 (2)	0.2334 (1)	0.0334 (4)
C5	0.0028 (4)	0.2679 (2)	0.2647 (2)	0.0363 (4)
C6	0.1126 (4)	0.3174 (2)	0.3651 (2)	0.0363 (4)
H1O1	0.3196	0.3578	0.5622	0.046
H1O2	−0.1619	0.1499	0.1026	0.040
HC5	−0.1745	0.3018	0.2143	0.036
HC6	0.0168	0.3879	0.3864	0.036

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0340 (3)	0.0503 (3)	0.0427 (3)	0.0103 (2)	−0.0001 (2)	0.0039 (2)
Cl2	0.0407 (3)	0.0389 (3)	0.0521 (4)	0.0050 (2)	0.0128 (2)	−0.0066 (2)
O1	0.0360 (8)	0.0620 (9)	0.0367 (7)	0.0060 (6)	0.0030 (6)	−0.0131 (7)
O2	0.0365 (7)	0.0492 (8)	0.0324 (7)	−0.0001 (6)	0.0044 (6)	−0.0040 (6)
C1	0.0291 (9)	0.0403 (9)	0.0316 (9)	−0.0004 (7)	0.0068 (7)	−0.0004 (7)
C2	0.0251 (8)	0.0374 (9)	0.0352 (9)	0.0018 (7)	0.0072 (7)	0.0040 (7)
C3	0.0281 (9)	0.0318 (8)	0.037 (1)	0.0001 (6)	0.0101 (7)	0.0009 (7)
C4	0.0302 (9)	0.0386 (9)	0.0306 (9)	−0.0049 (7)	0.0070 (7)	0.0018 (7)
C5	0.0314 (9)	0.040 (1)	0.036 (1)	0.0038 (7)	0.0061 (7)	0.0051 (8)
C6	0.031 (1)	0.039 (1)	0.039 (1)	0.0056 (7)	0.0097 (8)	0.0020 (8)

Geometric parameters (Å, º) top

Cl1—C2	1.721 (2)	C1—C6	1.386 (2)
Cl2—C3	1.727 (2)	C2—C3	1.389 (3)
O1—C1	1.372 (2)	C3—C4	1.392 (3)
O1—H1O1	1.000	C4—C5	1.383 (3)
O2—C4	1.374 (2)	C5—C6	1.383 (3)
O2—H1O2	1.000	C5—HC5	1.000
C1—C2	1.383 (3)	C6—HC6	1.000

C1—O1—H1O1	110.4	C2—C3—C4	120.1 (2)
C4—O2—H1O2	106.6	O2—C4—C3	118.2 (2)
O1—C1—C2	118.4 (2)	O2—C4—C5	122.4 (2)
O1—C1—C6	122.1 (2)	C3—C4—C5	119.4 (2)
C2—C1—C6	119.5 (2)	C4—C5—C6	120.4 (2)
Cl1—C2—C1	119.5 (1)	C4—C5—HC5	119.8
Cl1—C2—C3	120.3 (1)	C6—C5—HC5	119.8
C1—C2—C3	120.3 (2)	C1—C6—C5	120.3 (2)
Cl2—C3—C2	121.0 (1)	C1—C6—HC6	119.8
Cl2—C3—C4	118.9 (1)	C5—C6—HC6	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	1.00	1.84	2.794 (2)	158
O2—H1O2···O1ⁱⁱ	1.00	1.78	2.778 (2)	172

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

Experimental details

Crystal data
Chemical formula	C₆H₄Cl₂O₂
M_r	179.0
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	4.831 (1), 11.347 (2), 12.962 (3)
β (°)	105.94 (1)
V (Å³)	683.2 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	8.02
Crystal size (mm)	0.15 × 0.15 × 0.06

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Analytical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.33, 0.63
No. of measured, independent and observed [I > 2σ(I)] reflections	1449, 1290, 1187
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.050, 1.87
No. of reflections	1290
No. of parameters	92
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.31

Computer programs: CAD-4 Manual (Schagen et al., 1989), SIR92 (Altomare et al., 1994), RAELS (Rae, 2000), ORTEP-3 (Farrugia, 1997) and CrystalMaker (CrystalMaker Software, 2005), local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	1.00	1.84	2.794 (2)	158
O2—H1O2···O1ⁱⁱ	1.00	1.78	2.778 (2)	172

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

Acknowledgements

This research was supported by the Australian Research Council.

References

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