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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o636.
Published online 2009 February 28. doi:  10.1107/S1600536809004310
PMCID: PMC2968610

1,4-Dichloro­naphthalene-2,3-diol

Abstract

The achiral planar (maximum deviation 0.014 Å) title compound, C10H6Cl2O2, crystallizes in the chiral space group P212121 in an arrangement incorporating conventional O—H(...)O hydrogen bonding leading to a supra­molecular chain.

Related literature

For related structures, see: Ahn et al. (1995 [triangle], 1996 [triangle]). For the synthesis, see: Zincke & Fries (1904 [triangle]); Ahn et al. (1995 [triangle]). For related literature, see: Coppens & Hamilton (1970 [triangle]).

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Object name is e-65-0o636-scheme1.jpg

Experimental

Crystal data

  • C10H6Cl2O2
  • M r = 229.1
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o636-efi1.jpg
  • a = 5.0037 (4) Å
  • b = 11.589 (1) Å
  • c = 15.546 (2) Å
  • V = 901.5 (2) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 6.24 mm−1
  • T = 294 K
  • 0.32 × 0.09 × 0.09 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: analytical (de Meulenaer & Tompa, 1965 [triangle]) T min = 0.32, T max = 0.65
  • 1022 measured reflections
  • 1022 independent reflections
  • 958 reflections with I > 2σ(I)
  • 1 standard reflections frequency: 30 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.034
  • S = 1.38
  • 1022 reflections
  • 129 parameters
  • H-atom parameters not refined
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.17 e Å−3
  • Absolute structure: Flack (1983 [triangle]), no Friedel pairs
  • Flack parameter: 0.02 (1)

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004310/tk2370sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004310/tk2370Isup2.hkl

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

Acknowledgments

This research was supported by the Australian Research Council.

supplementary crystallographic information

Comment

1,4-Dichloronaphthalene-2,3-diol forms a 2:1 inclusion compound with dioxane, the structure of which (in space group P21/c) has been reported earlier (Ahn et al., 1995). However, crystallization from benzene, chloroform, diethyl ether, ethanol or methanol yields solvent-free material. The crystal structures of the isomeric 1,5-dichloronaphthalene-2,6-diol, and its 1:1 inclusion compound with dioxane, have also been described (Ahn et al., 1996); Fig. 1. The solvent-free title compound, (I), is planar and crystallizes such that each molecule takes part in only two hydrogen bonds (one as donor and one as acceptor), Table 1, with the same O1-hydroxy group being involved in both. This hydrogen bonding links molecules into a supramolecular chain in the a direction, with adjacent molecules along the chain being orthogonal. The O2—HO2 hydroxy group which does not take part in hydrogen bonding is directed towards an aromatic ring on another molecule to form an O2—HO2···π interaction with the shortest O2-H1O2···C3 and O2-H1O2···C4 distances of 2.50 and 2.58 Å, respectively. The molecules pack in a herringbone arrangement such that they are all perpendicular to the ab plane, maximizing opportunities for offset face-face and edge-face aromatic interactions. The former have an interplanar separation of ca 3.3 Å while for the latter, the C—H···C distances range up from 3.03 Å. Additionally, there are intermolecular Cl1···Cl2 interactions of 3.488 (2) Å and C—H···Cl interactions of 2.92, 3.04 and 3.09 Å and O—H···Cl of 3.05 Å.

Interestingly, this achiral molecule crystallizes in the chiral space group P212121. The 21 axis along a accommodates the hydrogen bonding linkage while that along b generates the chain of molecules linked by Cl1···Cl2 interactions. The 21 axis in the c direction leads to chains of almost coplanar molecules linked by pairs of C4—H4···Cl1 and C5—H5···Cl1 motifs.

Experimental

1,4-Dichloronaphthalene-2,3-diol was prepared as described (Zincke & Fries, 1904; Ahn et al., 1995) and X-ray quality solvent-free crystals were obtained from chloroform solution.

Refinement

Hydrogen 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.
Molecular structure of (I), showing the atom labeling scheme and displacement ellipsoids at the 50% probability level.

Crystal data

C10H6Cl2O2F(000) = 464.0
Mr = 229.1Dx = 1.69 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2abCell parameters from 10 reflections
a = 5.0037 (4) Åθ = 25–30°
b = 11.589 (1) ŵ = 6.24 mm1
c = 15.546 (2) ÅT = 294 K
V = 901.5 (2) Å3Prism, colourless
Z = 40.32 × 0.09 × 0.09 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0
ω–2θ scansθmax = 70°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)h = 0→6
Tmin = 0.32, Tmax = 0.65k = 0→14
1022 measured reflectionsl = 0→18
1022 independent reflections1 standard reflections every 30 min
958 reflections with I > 2σ(I) intensity decay: none

Refinement

Refinement on Fw = 1/[σ2(F) + 0.0004F2]
R[F2 > 2σ(F2)] = 0.022(Δ/σ)max = 0.007
wR(F2) = 0.034Δρmax = 0.18 e Å3
S = 1.38Δρmin = −0.17 e Å3
1022 reflectionsExtinction correction: (Coppens & Hamilton, 1970)
129 parametersExtinction coefficient: 1.3 (1)
0 restraintsAbsolute structure: Flack (1983), 0 Friedel pairs
H-atom parameters not refinedFlack parameter: 0.02 (1)

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

xyzUiso*/Ueq
Cl10.40159 (14)0.04588 (5)0.59724 (4)0.0414 (2)
Cl21.16627 (13)0.32908 (5)0.83291 (4)0.0412 (2)
O10.8036 (4)0.21135 (16)0.54315 (9)0.0402 (4)
O21.1352 (4)0.3308 (2)0.6420 (1)0.0424 (5)
C10.6113 (5)0.1220 (2)0.6655 (2)0.0290 (5)
C20.5913 (5)0.1058 (2)0.7565 (1)0.0293 (5)
C30.4048 (6)0.0300 (2)0.7943 (2)0.0344 (5)
C40.3944 (6)0.0166 (2)0.8827 (2)0.0408 (6)
C50.5719 (7)0.0785 (2)0.9350 (2)0.0435 (6)
C60.7518 (6)0.1537 (2)0.9010 (1)0.0376 (6)
C70.7679 (5)0.1700 (2)0.8102 (1)0.0300 (5)
C80.9496 (5)0.2466 (2)0.7716 (2)0.0308 (5)
C90.9652 (5)0.2599 (2)0.6839 (2)0.0306 (5)
C100.7904 (5)0.1964 (2)0.6298 (1)0.0303 (5)
H1O10.97260.24780.52210.040
H1O21.27040.36990.67930.042
H30.2790−0.01450.75690.034
H40.2609−0.03690.90910.041
H50.56600.06710.99870.043
H60.87370.19790.94000.038

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0418 (4)0.0482 (3)0.0341 (3)−0.0060 (3)−0.0095 (3)−0.0051 (2)
Cl20.0416 (4)0.0436 (3)0.0385 (3)−0.0083 (3)−0.0052 (3)−0.0080 (2)
O10.043 (1)0.055 (1)0.0226 (7)−0.0045 (9)−0.0010 (8)0.0052 (7)
O20.042 (1)0.0457 (9)0.0392 (9)−0.010 (1)0.0020 (8)0.0043 (7)
C10.027 (1)0.032 (1)0.027 (1)0.001 (1)−0.004 (1)−0.0023 (8)
C20.031 (1)0.030 (1)0.027 (1)0.003 (1)−0.001 (1)−0.0005 (8)
C30.033 (1)0.035 (1)0.036 (1)0.000 (1)0.002 (1)0.0010 (9)
C40.042 (2)0.043 (1)0.038 (1)−0.003 (1)0.008 (1)0.004 (1)
C50.051 (2)0.051 (1)0.028 (1)0.000 (1)0.006 (1)0.003 (1)
C60.044 (1)0.044 (1)0.025 (1)0.001 (1)−0.003 (1)−0.002 (1)
C70.032 (1)0.032 (1)0.026 (1)0.004 (1)0.000 (1)−0.0005 (9)
C80.031 (1)0.032 (1)0.030 (1)0.002 (1)−0.004 (1)−0.0046 (9)
C90.028 (1)0.031 (1)0.032 (1)0.001 (1)0.002 (1)0.0032 (9)
C100.032 (1)0.035 (1)0.0238 (9)0.006 (1)−0.002 (1)0.0002 (9)

Geometric parameters (Å, °)

Cl1—C11.734 (2)C6—C71.427 (3)
Cl2—C81.731 (2)C7—C81.405 (3)
O1—C101.361 (2)C8—C91.374 (3)
O2—C91.350 (3)C9—C101.419 (3)
C1—C21.431 (3)O1—H1O11.000
C1—C101.361 (3)O2—H1O21.000
C2—C31.410 (3)C3—H31.000
C2—C71.426 (3)C4—H41.000
C3—C41.385 (3)C5—H51.000
C4—C51.401 (4)C6—H61.000
C5—C61.360 (4)
Cl1—C1—C2119.7 (2)O2—C9—C8125.7 (2)
Cl1—C1—C10118.1 (2)O2—C9—C10114.7 (2)
C2—C1—C10122.2 (2)C8—C9—C10119.6 (2)
C1—C2—C3122.7 (2)O1—C10—C1121.1 (2)
C1—C2—C7117.8 (2)O1—C10—C9119.4 (2)
C3—C2—C7119.5 (2)C1—C10—C9119.6 (2)
C2—C3—C4120.5 (2)C10—O1—H1O1114.8
C3—C4—C5119.7 (3)C9—O2—H1O2115.0
C4—C5—C6121.5 (2)C4—C3—H3119.7
C5—C6—C7120.4 (2)C2—C3—H3119.7
C2—C7—C6118.4 (2)C3—C4—H4120.2
C2—C7—C8118.8 (2)C5—C4—H4120.2
C6—C7—C8122.9 (2)C4—C5—H5119.3
Cl2—C8—C7121.2 (2)C6—C5—H5119.3
Cl2—C8—C9116.7 (2)C5—C6—H6119.7
C7—C8—C9122.1 (2)C7—C6—H6119.9

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1O1···O1i1.002.002.977 (3)165

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2370).

References

  • Ahn, P. D., Bishop, R., Craig, D. C. & Scudder, M. L. (1995). J. Incl. Phenom. Mol. Rec. Chem.20, 267–276.
  • Ahn, P. D., Bishop, R., Craig, D. C. & Scudder, M. L. (1996). J. Incl. Phenom. Mol. Rec. Chem.23, 313–327.
  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.27, 435.
  • Coppens, P. & Hamilton, W. C. (1970). Acta Cryst. A26, 71–83.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Meulenaer, J. de & Tompa, H. (1965). Acta Cryst.19, 1014–1018.
  • Rae, A. D. (2000). RAELS Australian National University, Canberra.
  • Schagen, J. D., Straver, L., van Meurs, F. & Williams, G. (1989). CAD-4 Manual Enraf–Nonius, Delft, The Netherlands.
  • Zincke, T. & Fries, K. (1904). Annalen, 334, 342–366.

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