2,3-Dichloro­benzene-1,4-diol

Abstract

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,

• a = 4.831 (1) Å

• b = 11.347 (2) Å

• c = 12.962 (3) Å

• β = 105.94 (1)°

• V = 683.2 (2) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms attached to C were included at calculated positions (C—H = 1.0 Å). The hydroxy hydrogen atoms were located on a difference map, and were then fixed at a position along the OH vector with O—H = 1.0 Å. All hydrogen atoms were refined with isotropic thermal parameters equivalent to those of the atom to which they were bonded.

Figures

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.

Crystal data

C6H4Cl2O2	F(000) = 360.0
Mr = 179.0	Dx = 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

Enraf–Nonius CAD-4 diffractometer	Rint = 0.041
ω–2θ scans	θmax = 70°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −5→0
Tmin = 0.33, Tmax = 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

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	Δρmax = 0.42 e Å−3
92 parameters	Δρmin = −0.31 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.