5-Chloro-2-nitro­phenol

Ren, D.

doi:10.1107/S1600536812014638

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1365

doi:10.1107/S1600536812014638

Open

access

5-Chloro-2-nitrophenol

Dong-mei Ren ^a ^*

^aSecurity and Environment Engineering College, Capital University of Economics and Business, Beijing 10070, People's Republic of China
^*Correspondence e-mail: nanoren@126.com

(Received 1 April 2012; accepted 4 April 2012; online 13 April 2012)

The asymmetric unit of the title compound, C₆H₄ClNO₃, contains two independent molecules in which the dihedral angles between the benzene ring and the nitro groups are 2.5 (1) and 8.5 (1)°. Intramolecular O—H⋯O hydrogen bonds involving the hydroxy and nitro substituents result in the formation of S(6) six-membered rings. In the crystal, O—H⋯O, O—H⋯Cl and C—H⋯O hydrogen bonds together with Cl⋯O contacts [3.238 (3) and 3.207 (3) Å] generate a three-dimensional network.

Related literature

For background to applications of the title compound and its synthesis, see: Richard (1971 ). For bond-length data, see: Allen et al. (1987 ) and for hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₄ClNO₃
M_r = 173.55
Triclinic, $[P \overline 1]$
a = 7.5390 (15) Å
b = 8.1640 (16) Å
c = 13.132 (3) Å
α = 94.75 (3)°
β = 96.48 (3)°
γ = 116.46 (3)°
V = 710.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.909, T_max = 0.953
2808 measured reflections
2596 independent reflections
1833 reflections with I > 2σ(I)
R_int = 0.075
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.171
S = 1.01
2596 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2	0.82	1.91	2.605 (5)	142
O6—H6A⋯O4	0.82	1.88	2.581 (4)	143
O3—H3A⋯O6ⁱ	0.82	2.71	3.350 (5)	136
O6—H6A⋯Cl2ⁱⁱ	0.82	2.70	3.207 (3)	121
C2—H2A⋯O5ⁱⁱⁱ	0.93	2.49	3.155 (5)	129
Symmetry codes: (i) -x+1, -y, -z+2; (ii) x, y-1, z; (iii) -x+1, -y, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014638/sj5233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014638/sj5233Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812014638/sj5233Isup3.cml

checkCIF report

Comment top

The title compound, 5-chloro-2-nitrophenol, is an important intermediate in the preparation of commercially important materials such as lamprecides, agricultural chemicals and dyestuffs (Richard, 1971). We report here the crystal structure of the title compound, (I).

The asymmetric unit contains two molecules of 5-chloro-2-nitrophenol, Fig. 1. The dihedral angles between the C1—C6 ring plane and that of the nitro group N1/O1/O2 is 2.5 (1)° while that between the C7—C12 plane and that of N2/04/05 is 8.5 (1)°. Intramolecular O3—H3A···O2 and O6—H6A···O4 hydrogen bonds form S(6) rings in both molecules (Bernstein et al., 1995). Bond distances in both molecules are normal (Allen et al. 1987).

In the crystal structure intermolecular O—H···O, O—H···Cl, and C—H···O hydrogen bonds, Table 1, together with and Cl2···O2 and Cl2···O6 contacts with distances 3.238 (3) and 3.207 (3) Å respectively generate a three dimensional network structure, Fig 2.

Related literature top

The title compound is an important intermediate in organic synthesis. For background to applications of the title compound and its synthesis, see: Richard (1971). For bond-length data, see: Allen et al. (1987) and for hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Richard, 1971). Crystals were obtained by dissolving (I) (0.1 g) in methanol (30 ml) and evaporating the solvent slowly at room temperature for about 8 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and intramolecular hydrogen bonds are drawn as dashed lines.
	Fig. 2. A packing diagram for (I) with hydrogen bonds drawn as dashed lines.

5-Chloro-2-nitrophenol top

Crystal data top

C₆H₄ClNO₃	Z = 4
M_r = 173.55	F(000) = 352
Triclinic, P1	D_x = 1.622 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5390 (15) Å	Cell parameters from 25 reflections
b = 8.1640 (16) Å	θ = 9–13°
c = 13.132 (3) Å	µ = 0.49 mm⁻¹
α = 94.75 (3)°	T = 293 K
β = 96.48 (3)°	Block, colourless
γ = 116.46 (3)°	0.20 × 0.10 × 0.10 mm
V = 710.9 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1833 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.075
Graphite monochromator	θ_max = 25.4°, θ_min = 1.6°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −9→8
T_min = 0.909, T_max = 0.953	l = −15→15
2808 measured reflections	3 standard reflections every 200 reflections
2596 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.1P)² + 0.250P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2596 reflections	Δρ_max = 0.32 e Å⁻³
200 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.45 (3)

Crystal data top

C₆H₄ClNO₃	γ = 116.46 (3)°
M_r = 173.55	V = 710.9 (2) Å³
Triclinic, P1	Z = 4
a = 7.5390 (15) Å	Mo Kα radiation
b = 8.1640 (16) Å	µ = 0.49 mm⁻¹
c = 13.132 (3) Å	T = 293 K
α = 94.75 (3)°	0.20 × 0.10 × 0.10 mm
β = 96.48 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1833 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.075
T_min = 0.909, T_max = 0.953	3 standard reflections every 200 reflections
2808 measured reflections	intensity decay: 1%
2596 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.01	Δρ_max = 0.32 e Å⁻³
2596 reflections	Δρ_min = −0.36 e Å⁻³
200 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cl1	0.09701 (18)	−0.12155 (17)	0.84727 (9)	0.0829 (5)
O1	0.9021 (5)	0.6279 (4)	1.0905 (2)	0.0826 (10)
O2	0.7781 (5)	0.5201 (4)	1.2241 (2)	0.0782 (9)
O3	0.4570 (5)	0.2037 (4)	1.2061 (2)	0.0767 (9)
H3A	0.5526	0.2962	1.2398	0.115*
N1	0.7735 (5)	0.5097 (4)	1.1288 (3)	0.0597 (8)
C1	0.4447 (6)	0.2008 (6)	0.8902 (3)	0.0629 (11)
H1A	0.4394	0.1959	0.8188	0.075*
C2	0.5999 (6)	0.3446 (5)	0.9564 (3)	0.0583 (10)
H2A	0.7001	0.4381	0.9299	0.070*
C3	0.6081 (5)	0.3513 (5)	1.0626 (3)	0.0489 (8)
C4	0.4593 (6)	0.2115 (5)	1.1042 (3)	0.0539 (9)
C5	0.3021 (6)	0.0657 (5)	1.0360 (3)	0.0580 (10)
H5A	0.2021	−0.0294	1.0617	0.070*
C6	0.2954 (6)	0.0625 (5)	0.9309 (3)	0.0590 (10)
Cl2	0.29044 (16)	0.23975 (12)	0.58973 (8)	0.0630 (4)
O4	0.1840 (5)	−0.5736 (4)	0.3805 (2)	0.0739 (9)
O5	0.2094 (5)	−0.4362 (4)	0.2464 (2)	0.0739 (9)
O6	0.2463 (5)	−0.3927 (4)	0.5626 (2)	0.0687 (8)
H6A	0.2295	−0.4825	0.5222	0.103*
N2	0.2030 (5)	−0.4369 (4)	0.3381 (2)	0.0540 (8)
C7	0.2170 (5)	−0.1315 (5)	0.3516 (3)	0.0497 (9)
H7A	0.2034	−0.1425	0.2798	0.060*
C8	0.2359 (5)	0.0268 (5)	0.4076 (3)	0.0506 (9)
H8A	0.2334	0.1225	0.3746	0.061*
C9	0.2591 (5)	0.0401 (4)	0.5151 (3)	0.0460 (8)
C10	0.2595 (5)	−0.1007 (5)	0.5650 (3)	0.0481 (8)
H10A	0.2723	−0.0890	0.6368	0.058*
C11	0.2407 (5)	−0.2611 (5)	0.5086 (3)	0.0474 (8)
C12	0.2176 (5)	−0.2746 (4)	0.4005 (2)	0.0440 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0728 (8)	0.0827 (8)	0.0728 (8)	0.0264 (6)	−0.0025 (6)	−0.0195 (6)
O1	0.085 (2)	0.0652 (19)	0.070 (2)	0.0088 (16)	0.0131 (16)	0.0168 (15)
O2	0.095 (2)	0.0759 (19)	0.0435 (17)	0.0233 (17)	0.0098 (14)	−0.0014 (13)
O3	0.093 (2)	0.0755 (19)	0.0431 (15)	0.0196 (16)	0.0213 (14)	0.0132 (13)
N1	0.070 (2)	0.0529 (18)	0.054 (2)	0.0260 (17)	0.0112 (16)	0.0083 (15)
C1	0.082 (3)	0.068 (3)	0.038 (2)	0.033 (2)	0.0116 (18)	0.0072 (18)
C2	0.070 (2)	0.058 (2)	0.046 (2)	0.027 (2)	0.0173 (18)	0.0112 (17)
C3	0.060 (2)	0.0470 (19)	0.0414 (18)	0.0262 (17)	0.0073 (16)	0.0053 (15)
C4	0.066 (2)	0.059 (2)	0.0397 (19)	0.0295 (19)	0.0159 (16)	0.0077 (16)
C5	0.063 (2)	0.053 (2)	0.057 (2)	0.0231 (19)	0.0211 (18)	0.0118 (17)
C6	0.063 (2)	0.059 (2)	0.056 (2)	0.032 (2)	0.0067 (18)	−0.0028 (18)
Cl2	0.0752 (7)	0.0489 (6)	0.0650 (7)	0.0330 (5)	0.0030 (5)	−0.0050 (4)
O4	0.114 (3)	0.0442 (15)	0.0637 (18)	0.0359 (16)	0.0214 (16)	0.0060 (13)
O5	0.099 (2)	0.0729 (19)	0.0451 (16)	0.0352 (17)	0.0187 (14)	−0.0026 (13)
O6	0.113 (2)	0.0499 (15)	0.0509 (16)	0.0420 (16)	0.0173 (15)	0.0176 (12)
N2	0.0596 (19)	0.0457 (17)	0.0481 (18)	0.0176 (14)	0.0108 (14)	−0.0003 (13)
C7	0.054 (2)	0.051 (2)	0.0372 (18)	0.0180 (17)	0.0070 (15)	0.0076 (15)
C8	0.057 (2)	0.0414 (18)	0.052 (2)	0.0206 (16)	0.0084 (16)	0.0141 (15)
C9	0.0472 (19)	0.0419 (18)	0.0468 (19)	0.0198 (15)	0.0061 (15)	0.0022 (14)
C10	0.058 (2)	0.0481 (19)	0.0352 (17)	0.0223 (17)	0.0073 (15)	0.0050 (14)
C11	0.058 (2)	0.0421 (18)	0.0399 (18)	0.0186 (16)	0.0129 (15)	0.0115 (14)
C12	0.0454 (19)	0.0372 (17)	0.0412 (18)	0.0112 (14)	0.0101 (14)	0.0055 (14)

Geometric parameters (Å, º) top

Cl1—C6	1.748 (4)	Cl2—C9	1.736 (3)
O1—N1	1.217 (4)	O4—N2	1.247 (4)
O2—N1	1.242 (4)	O5—N2	1.210 (4)
O3—C4	1.347 (4)	O6—C11	1.349 (4)
O3—H3A	0.8200	O6—H6A	0.8200
N1—C3	1.454 (5)	N2—C12	1.452 (4)
C1—C2	1.371 (5)	C7—C8	1.373 (5)
C1—C6	1.389 (6)	C7—C12	1.380 (5)
C1—H1A	0.9300	C7—H7A	0.9300
C2—C3	1.385 (5)	C8—C9	1.392 (5)
C2—H2A	0.9300	C8—H8A	0.9300
C3—C4	1.399 (5)	C9—C10	1.370 (5)
C4—C5	1.397 (6)	C10—C11	1.391 (5)
C5—C6	1.373 (5)	C10—H10A	0.9300
C5—H5A	0.9300	C11—C12	1.399 (5)

C4—O3—H3A	109.5	C11—O6—H6A	109.5
O1—N1—O2	121.8 (3)	O5—N2—O4	121.6 (3)
O1—N1—C3	120.0 (3)	O5—N2—C12	119.3 (3)
O2—N1—C3	118.2 (3)	O4—N2—C12	119.0 (3)
C2—C1—C6	119.2 (3)	C8—C7—C12	120.9 (3)
C2—C1—H1A	120.4	C8—C7—H7A	119.5
C6—C1—H1A	120.4	C12—C7—H7A	119.5
C1—C2—C3	120.3 (4)	C7—C8—C9	118.1 (3)
C1—C2—H2A	119.8	C7—C8—H8A	121.0
C3—C2—H2A	119.8	C9—C8—H8A	121.0
C2—C3—C4	120.7 (3)	C10—C9—C8	121.8 (3)
C2—C3—N1	117.8 (3)	C10—C9—Cl2	118.3 (3)
C4—C3—N1	121.5 (3)	C8—C9—Cl2	119.9 (3)
O3—C4—C5	116.6 (3)	C9—C10—C11	120.3 (3)
O3—C4—C3	125.0 (3)	C9—C10—H10A	119.9
C5—C4—C3	118.4 (3)	C11—C10—H10A	119.9
C6—C5—C4	120.0 (4)	O6—C11—C10	117.2 (3)
C6—C5—H5A	120.0	O6—C11—C12	124.8 (3)
C4—C5—H5A	120.0	C10—C11—C12	118.0 (3)
C5—C6—C1	121.3 (4)	C7—C12—C11	120.9 (3)
C5—C6—Cl1	119.1 (3)	C7—C12—N2	118.8 (3)
C1—C6—Cl1	119.7 (3)	C11—C12—N2	120.2 (3)

C6—C1—C2—C3	0.3 (6)	C12—C7—C8—C9	1.0 (5)
C1—C2—C3—C4	0.3 (6)	C7—C8—C9—C10	−1.2 (5)
C1—C2—C3—N1	−178.4 (4)	C7—C8—C9—Cl2	178.3 (3)
O1—N1—C3—C2	−2.3 (5)	C8—C9—C10—C11	1.4 (5)
O2—N1—C3—C2	177.5 (4)	Cl2—C9—C10—C11	−178.1 (3)
O1—N1—C3—C4	179.0 (4)	C9—C10—C11—O6	178.7 (3)
O2—N1—C3—C4	−1.2 (5)	C9—C10—C11—C12	−1.3 (5)
C2—C3—C4—O3	178.3 (4)	C8—C7—C12—C11	−0.9 (5)
N1—C3—C4—O3	−3.0 (6)	C8—C7—C12—N2	−178.2 (3)
C2—C3—C4—C5	−0.2 (5)	O6—C11—C12—C7	−178.9 (3)
N1—C3—C4—C5	178.5 (3)	C10—C11—C12—C7	1.0 (5)
O3—C4—C5—C6	−179.2 (4)	O6—C11—C12—N2	−1.6 (5)
C3—C4—C5—C6	−0.5 (6)	C10—C11—C12—N2	178.3 (3)
C4—C5—C6—C1	1.2 (6)	O5—N2—C12—C7	6.9 (5)
C4—C5—C6—Cl1	−180.0 (3)	O4—N2—C12—C7	−173.2 (3)
C2—C1—C6—C5	−1.1 (6)	O5—N2—C12—C11	−170.4 (3)
C2—C1—C6—Cl1	−179.9 (3)	O4—N2—C12—C11	9.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.82	1.91	2.605 (5)	142
O6—H6A···O4	0.82	1.88	2.581 (4)	143
O3—H3A···O6ⁱ	0.82	2.71	3.350 (5)	136
O6—H6A···Cl2ⁱⁱ	0.82	2.70	3.207 (3)	121
C2—H2A···O5ⁱⁱⁱ	0.93	2.49	3.155 (5)	129

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, y−1, z; (iii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₆H₄ClNO₃
M_r	173.55
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5390 (15), 8.1640 (16), 13.132 (3)
α, β, γ (°)	94.75 (3), 96.48 (3), 116.46 (3)
V (Å³)	710.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.909, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	2808, 2596, 1833
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.171, 1.01
No. of reflections	2596
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.36

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.8200	1.9100	2.605 (5)	142.00
O6—H6A···O4	0.8200	1.8800	2.581 (4)	143.00
O3—H3A···O6ⁱ	0.8200	2.7130	3.350 (5)	136.00
O6—H6A···Cl2ⁱⁱ	0.8200	2.7000	3.207 (3)	121.00
C2—H2A···O5ⁱⁱⁱ	0.9300	2.4900	3.155 (5)	129.00

Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, y−1, z; (iii) −x+1, −y, −z+1.

Acknowledgements

This study was supported financially by the Capital University of Economics and Business (00891162721716) and the Scientific Research Level Project of the Beijing Education Commission Foundation. The author thanks the Center of Testing and Analysis, Beijing University of Science and Technology, for the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Richard, L. J. (1971). J. Org. Chem. 36, 242–243. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar