1,4-Dichloro­naphthalene-2,3-diol

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

doi:10.1107/S1600536809004310

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o636

doi:10.1107/S1600536809004310

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1,4-Dichloronaphthalene-2,3-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, Australia 2052
^*Correspondence e-mail: m.scudder@unsw.edu.au

(Received 2 February 2009; accepted 5 February 2009; online 28 February 2009)

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

Experimental

Crystal data

C₁₀H₆Cl₂O₂
M_r = 229.1
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.022
wR(F²) = 0.034
S = 1.38
1022 reflections
129 parameters
H-atom parameters not refined
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), no Friedel pairs
Flack parameter: 0.02 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O1ⁱ	1.00	2.00	2.977 (3)	165
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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 ); software used to prepare material for publication: local programs.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

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: ORTEPII (Farrugia, 1997); software used to prepare material for publication: local programs.

Figures top

Fig. 1. Molecular structure of (I), showing the atom labeling scheme and displacement ellipsoids at the 50% probability level.

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

Crystal data top

C₁₀H₆Cl₂O₂	F(000) = 464.0
M_r = 229.1	D_x = 1.69 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10 reflections
a = 5.0037 (4) Å	θ = 25–30°
b = 11.589 (1) Å	µ = 6.24 mm⁻¹
c = 15.546 (2) Å	T = 294 K
V = 901.5 (2) Å³	Prism, colourless
Z = 4	0.32 × 0.09 × 0.09 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0
ω–2θ scans	θ_max = 70°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = 0→6
T_min = 0.32, T_max = 0.65	k = 0→14
1022 measured reflections	l = 0→18
1022 independent reflections	1 standard reflections every 30 min
958 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F	w = 1/[σ²(F) + 0.0004F²]
R[F² > 2σ(F²)] = 0.022	(Δ/σ)_max = 0.007
wR(F²) = 0.034	Δρ_max = 0.18 e Å⁻³
S = 1.38	Δρ_min = −0.17 e Å⁻³
1022 reflections	Extinction correction: (Coppens & Hamilton, 1970)
129 parameters	Extinction coefficient: 1.3 (1)
0 restraints	Absolute structure: Flack (1983), 0 Friedel pairs
H-atom parameters not refined	Absolute structure parameter: 0.02 (1)

Crystal data top

C₁₀H₆Cl₂O₂	V = 901.5 (2) Å³
M_r = 229.1	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 5.0037 (4) Å	µ = 6.24 mm⁻¹
b = 11.589 (1) Å	T = 294 K
c = 15.546 (2) Å	0.32 × 0.09 × 0.09 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	958 reflections with I > 2σ(I)
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	R_int = 0
T_min = 0.32, T_max = 0.65	1 standard reflections every 30 min
1022 measured reflections	intensity decay: none
1022 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	H-atom parameters not refined
wR(F²) = 0.034	Δρ_max = 0.18 e Å⁻³
S = 1.38	Δρ_min = −0.17 e Å⁻³
1022 reflections	Absolute structure: Flack (1983), 0 Friedel pairs
129 parameters	Absolute structure parameter: 0.02 (1)
0 restraints

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

	x	y	z	U_iso*/U_eq
Cl1	0.40159 (14)	0.04588 (5)	0.59724 (4)	0.0414 (2)
Cl2	1.16627 (13)	0.32908 (5)	0.83291 (4)	0.0412 (2)
O1	0.8036 (4)	0.21135 (16)	0.54315 (9)	0.0402 (4)
O2	1.1352 (4)	0.3308 (2)	0.6420 (1)	0.0424 (5)
C1	0.6113 (5)	0.1220 (2)	0.6655 (2)	0.0290 (5)
C2	0.5913 (5)	0.1058 (2)	0.7565 (1)	0.0293 (5)
C3	0.4048 (6)	0.0300 (2)	0.7943 (2)	0.0344 (5)
C4	0.3944 (6)	0.0166 (2)	0.8827 (2)	0.0408 (6)
C5	0.5719 (7)	0.0785 (2)	0.9350 (2)	0.0435 (6)
C6	0.7518 (6)	0.1537 (2)	0.9010 (1)	0.0376 (6)
C7	0.7679 (5)	0.1700 (2)	0.8102 (1)	0.0300 (5)
C8	0.9496 (5)	0.2466 (2)	0.7716 (2)	0.0308 (5)
C9	0.9652 (5)	0.2599 (2)	0.6839 (2)	0.0306 (5)
C10	0.7904 (5)	0.1964 (2)	0.6298 (1)	0.0303 (5)
H1O1	0.9726	0.2478	0.5221	0.040
H1O2	1.2704	0.3699	0.6793	0.042
H3	0.2790	−0.0145	0.7569	0.034
H4	0.2609	−0.0369	0.9091	0.041
H5	0.5660	0.0671	0.9987	0.043
H6	0.8737	0.1979	0.9400	0.038

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0418 (4)	0.0482 (3)	0.0341 (3)	−0.0060 (3)	−0.0095 (3)	−0.0051 (2)
Cl2	0.0416 (4)	0.0436 (3)	0.0385 (3)	−0.0083 (3)	−0.0052 (3)	−0.0080 (2)
O1	0.043 (1)	0.055 (1)	0.0226 (7)	−0.0045 (9)	−0.0010 (8)	0.0052 (7)
O2	0.042 (1)	0.0457 (9)	0.0392 (9)	−0.010 (1)	0.0020 (8)	0.0043 (7)
C1	0.027 (1)	0.032 (1)	0.027 (1)	0.001 (1)	−0.004 (1)	−0.0023 (8)
C2	0.031 (1)	0.030 (1)	0.027 (1)	0.003 (1)	−0.001 (1)	−0.0005 (8)
C3	0.033 (1)	0.035 (1)	0.036 (1)	0.000 (1)	0.002 (1)	0.0010 (9)
C4	0.042 (2)	0.043 (1)	0.038 (1)	−0.003 (1)	0.008 (1)	0.004 (1)
C5	0.051 (2)	0.051 (1)	0.028 (1)	0.000 (1)	0.006 (1)	0.003 (1)
C6	0.044 (1)	0.044 (1)	0.025 (1)	0.001 (1)	−0.003 (1)	−0.002 (1)
C7	0.032 (1)	0.032 (1)	0.026 (1)	0.004 (1)	0.000 (1)	−0.0005 (9)
C8	0.031 (1)	0.032 (1)	0.030 (1)	0.002 (1)	−0.004 (1)	−0.0046 (9)
C9	0.028 (1)	0.031 (1)	0.032 (1)	0.001 (1)	0.002 (1)	0.0032 (9)
C10	0.032 (1)	0.035 (1)	0.0238 (9)	0.006 (1)	−0.002 (1)	0.0002 (9)

Geometric parameters (Å, º) top

Cl1—C1	1.734 (2)	C6—C7	1.427 (3)
Cl2—C8	1.731 (2)	C7—C8	1.405 (3)
O1—C10	1.361 (2)	C8—C9	1.374 (3)
O2—C9	1.350 (3)	C9—C10	1.419 (3)
C1—C2	1.431 (3)	O1—H1O1	1.000
C1—C10	1.361 (3)	O2—H1O2	1.000
C2—C3	1.410 (3)	C3—H3	1.000
C2—C7	1.426 (3)	C4—H4	1.000
C3—C4	1.385 (3)	C5—H5	1.000
C4—C5	1.401 (4)	C6—H6	1.000
C5—C6	1.360 (4)

Cl1—C1—C2	119.7 (2)	O2—C9—C8	125.7 (2)
Cl1—C1—C10	118.1 (2)	O2—C9—C10	114.7 (2)
C2—C1—C10	122.2 (2)	C8—C9—C10	119.6 (2)
C1—C2—C3	122.7 (2)	O1—C10—C1	121.1 (2)
C1—C2—C7	117.8 (2)	O1—C10—C9	119.4 (2)
C3—C2—C7	119.5 (2)	C1—C10—C9	119.6 (2)
C2—C3—C4	120.5 (2)	C10—O1—H1O1	114.8
C3—C4—C5	119.7 (3)	C9—O2—H1O2	115.0
C4—C5—C6	121.5 (2)	C4—C3—H3	119.7
C5—C6—C7	120.4 (2)	C2—C3—H3	119.7
C2—C7—C6	118.4 (2)	C3—C4—H4	120.2
C2—C7—C8	118.8 (2)	C5—C4—H4	120.2
C6—C7—C8	122.9 (2)	C4—C5—H5	119.3
Cl2—C8—C7	121.2 (2)	C6—C5—H5	119.3
Cl2—C8—C9	116.7 (2)	C5—C6—H6	119.7
C7—C8—C9	122.1 (2)	C7—C6—H6	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1ⁱ	1.00	2.00	2.977 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₁₀H₆Cl₂O₂
M_r	229.1
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	5.0037 (4), 11.589 (1), 15.546 (2)
V (Å³)	901.5 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	6.24
Crystal size (mm)	0.32 × 0.09 × 0.09

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Analytical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.32, 0.65
No. of measured, independent and observed [I > 2σ(I)] reflections	1022, 1022, 958
R_int	0
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.034, 1.38
No. of reflections	1022
No. of parameters	129
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17
Absolute structure	Flack (1983), 0 Friedel pairs
Absolute structure parameter	0.02 (1)

Computer programs: CAD-4 Manual (Schagen et al., 1989), SIR92 (Altomare et al., 1994), RAELS (Rae, 2000), ORTEPII (Farrugia, 1997), local programs.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1ⁱ	1.00	2.00	2.977 (3)	165

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

Acknowledgements

This research was supported by the Australian Research Council.

References

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