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 ▶, 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,

• a = 5.0037 (4) Å

• b = 11.589 (1) Å

• c = 15.546 (2) Å

• V = 901.5 (2) ų

• 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[F ² > 2σ(F ²)] = 0.022

• wR(F ²) = 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)

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.

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⋯O1i	1.00	2.00	2.977 (3)	165

Symmetry code: (i) .

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

C10H6Cl2O2	F(000) = 464.0
Mr = 229.1	Dx = 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

Enraf–Nonius CAD-4 diffractometer	Rint = 0
ω–2θ scans	θmax = 70°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = 0→6
Tmin = 0.32, Tmax = 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

Refinement on F	w = 1/[σ2(F) + 0.0004F2]
R[F2 > 2σ(F2)] = 0.022	(Δ/σ)max = 0.007
wR(F2) = 0.034	Δρmax = 0.18 e Å−3
S = 1.38	Δρmin = −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	Flack parameter: 0.02 (1)

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

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