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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1103

2,3-Di­chloro­benzene-1,4-diol

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[Ahn, P. D., Bishop, R., Craig, D. C. & Scudder, M. L. (1995). J. Incl. Phenom. Mol. Rec. Chem. 20, 267-276.], 1996[Ahn, P. D., Bishop, R., Craig, D. C. & Scudder, M. L. (1996). J. Incl. Phenom. Mol. Rec. Chem. 23, 313-327.]). For the preparation of the title compound, see: Beddoes et al. (1981[Beddoes, R. L., Bruce, J. M., Finch, H., Heelam, L. M. J., Hunt, I. D. & Mills, O. S. (1981). J. Chem. Soc. Perkin Trans. 1, pp. 2670-2676.]).

[Scheme 1]

Experimental

Crystal data
  • C6H4Cl2O2

  • Mr = 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[Meulenaer, J. de & Tompa, H. (1965). Acta Cryst. 19, 1014-1018.]) Tmin = 0.33, Tmax = 0.63

  • 1449 measured reflections

  • 1290 independent reflections

  • 1187 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.42 e Å−3

  • Δρmin = −0.31 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Schagen, J. D., Straver, L., van Meurs, F. & Williams, G. (1989). CAD-4 Manual. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Manual; data reduction: local program; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: RAELS (Rae, 2000[Rae, A. D. (2000). RAELS. Australian National University, Canberra, Australia.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and CrystalMaker (CrystalMaker Software, 2005[CrystalMaker Software (2005). CrystalMaker. CrystalMaker Software, Yarnton, England. www.CrystalMaker.co.uk.]); software used to prepare material for publication: local programs.

Supporting information


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.

Refinement top

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.

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
[Figure 1] Fig. 1. A molecule of the title compound, showing atom labelling. Thermal ellipsoids are drawn at the 50% level.
[Figure 2] 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
C6H4Cl2O2F(000) = 360.0
Mr = 179.0Dx = 1.74 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
a = 4.831 (1) ÅCell parameters from 10 reflections
b = 11.347 (2) Åθ = 25–30°
c = 12.962 (3) ŵ = 8.02 mm1
β = 105.94 (1)°T = 294 K
V = 683.2 (2) Å3Tabular, colourless
Z = 40.15 × 0.15 × 0.06 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
Rint = 0.041
ω–2θ scansθmax = 70°
Absorption correction: analytical
(de Meulenaer & Tompa, 1965)
h = 50
Tmin = 0.33, Tmax = 0.63k = 130
1449 measured reflectionsl = 1515
1290 independent reflections1 standard reflections every 30 min
1187 reflections with I > 2σ(I) intensity decay: 21%
Refinement top
Refinement on F0 restraints
R[F2 > 2σ(F2)] = 0.034H-atom parameters not refined
wR(F2) = 0.050 w = 1/[σ2(F) + 0.0004F2]
S = 1.87(Δ/σ)max = 0.008
1290 reflectionsΔρmax = 0.42 e Å3
92 parametersΔρmin = 0.31 e Å3
Crystal data top
C6H4Cl2O2V = 683.2 (2) Å3
Mr = 179.0Z = 4
Monoclinic, P21/cCu Kα radiation
a = 4.831 (1) ŵ = 8.02 mm1
b = 11.347 (2) ÅT = 294 K
c = 12.962 (3) Å0.15 × 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)
Rint = 0.041
Tmin = 0.33, Tmax = 0.631 standard reflections every 30 min
1449 measured reflections intensity decay: 21%
1290 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.050H-atom parameters not refined
S = 1.87Δρmax = 0.42 e Å3
1290 reflectionsΔρmin = 0.31 e Å3
92 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.78228 (10)0.11149 (4)0.49607 (4)0.0444 (2)
Cl20.54566 (11)0.00422 (4)0.26478 (4)0.0439 (2)
O10.4715 (3)0.3170 (1)0.5364 (1)0.0463 (4)
O20.0408 (3)0.1224 (1)0.1331 (1)0.0404 (4)
C10.3548 (4)0.2698 (2)0.4364 (2)0.0340 (4)
C20.4868 (4)0.1726 (2)0.4063 (1)0.0328 (4)
C30.3797 (4)0.1238 (2)0.3049 (2)0.0319 (4)
C40.1366 (4)0.1719 (2)0.2334 (1)0.0334 (4)
C50.0028 (4)0.2679 (2)0.2647 (2)0.0363 (4)
C60.1126 (4)0.3174 (2)0.3651 (2)0.0363 (4)
H1O10.31960.35780.56220.046
H1O20.16190.14990.10260.040
HC50.17450.30180.21430.036
HC60.01680.38790.38640.036
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0340 (3)0.0503 (3)0.0427 (3)0.0103 (2)0.0001 (2)0.0039 (2)
Cl20.0407 (3)0.0389 (3)0.0521 (4)0.0050 (2)0.0128 (2)0.0066 (2)
O10.0360 (8)0.0620 (9)0.0367 (7)0.0060 (6)0.0030 (6)0.0131 (7)
O20.0365 (7)0.0492 (8)0.0324 (7)0.0001 (6)0.0044 (6)0.0040 (6)
C10.0291 (9)0.0403 (9)0.0316 (9)0.0004 (7)0.0068 (7)0.0004 (7)
C20.0251 (8)0.0374 (9)0.0352 (9)0.0018 (7)0.0072 (7)0.0040 (7)
C30.0281 (9)0.0318 (8)0.037 (1)0.0001 (6)0.0101 (7)0.0009 (7)
C40.0302 (9)0.0386 (9)0.0306 (9)0.0049 (7)0.0070 (7)0.0018 (7)
C50.0314 (9)0.040 (1)0.036 (1)0.0038 (7)0.0061 (7)0.0051 (8)
C60.031 (1)0.039 (1)0.039 (1)0.0056 (7)0.0097 (8)0.0020 (8)
Geometric parameters (Å, º) top
Cl1—C21.721 (2)C1—C61.386 (2)
Cl2—C31.727 (2)C2—C31.389 (3)
O1—C11.372 (2)C3—C41.392 (3)
O1—H1O11.000C4—C51.383 (3)
O2—C41.374 (2)C5—C61.383 (3)
O2—H1O21.000C5—HC51.000
C1—C21.383 (3)C6—HC61.000
C1—O1—H1O1110.4C2—C3—C4120.1 (2)
C4—O2—H1O2106.6O2—C4—C3118.2 (2)
O1—C1—C2118.4 (2)O2—C4—C5122.4 (2)
O1—C1—C6122.1 (2)C3—C4—C5119.4 (2)
C2—C1—C6119.5 (2)C4—C5—C6120.4 (2)
Cl1—C2—C1119.5 (1)C4—C5—HC5119.8
Cl1—C2—C3120.3 (1)C6—C5—HC5119.8
C1—C2—C3120.3 (2)C1—C6—C5120.3 (2)
Cl2—C3—C2121.0 (1)C1—C6—HC6119.8
Cl2—C3—C4118.9 (1)C5—C6—HC6119.8
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O2i1.001.842.794 (2)158
O2—H1O2···O1ii1.001.782.778 (2)172
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC6H4Cl2O2
Mr179.0
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)4.831 (1), 11.347 (2), 12.962 (3)
β (°) 105.94 (1)
V3)683.2 (2)
Z4
Radiation typeCu Kα
µ (mm1)8.02
Crystal size (mm)0.15 × 0.15 × 0.06
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionAnalytical
(de Meulenaer & Tompa, 1965)
Tmin, Tmax0.33, 0.63
No. of measured, independent and
observed [I > 2σ(I)] reflections
1449, 1290, 1187
Rint0.041
(sin θ/λ)max1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.050, 1.87
No. of reflections1290
No. of parameters92
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1O1···O2i1.001.842.794 (2)158
O2—H1O2···O1ii1.001.782.778 (2)172
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1, y+1/2, z1/2.
 

Acknowledgements

This research was supported by the Australian Research Council.

References

First citationAhn, P. D., Bishop, R., Craig, D. C. & Scudder, M. L. (1995). J. Incl. Phenom. Mol. Rec. Chem. 20, 267–276.  CrossRef Google Scholar
First citationAhn, P. D., Bishop, R., Craig, D. C. & Scudder, M. L. (1996). J. Incl. Phenom. Mol. Rec. Chem. 23, 313–327.  CSD CrossRef Google Scholar
First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals Google Scholar
First citationBeddoes, R. L., Bruce, J. M., Finch, H., Heelam, L. M. J., Hunt, I. D. & Mills, O. S. (1981). J. Chem. Soc. Perkin Trans. 1, pp. 2670–2676.  CrossRef Web of Science Google Scholar
First citationCrystalMaker Software (2005). CrystalMaker. CrystalMaker Software, Yarnton, England. www.CrystalMaker.co.uk.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationMeulenaer, J. de & Tompa, H. (1965). Acta Cryst. 19, 1014–1018.  CrossRef IUCr Journals Web of Science Google Scholar
First citationRae, A. D. (2000). RAELS. Australian National University, Canberra, Australia.  Google Scholar
First citationSchagen, J. D., Straver, L., van Meurs, F. & Williams, G. (1989). CAD-4 Manual. Enraf–Nonius, Delft, The Netherlands.  Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1103
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