2-Chloro-4-(3,3-dichloro­all­yloxy)-1-nitro­benzene

Yu, X.; Xia, Z.; Li, C.

doi:10.1107/S160053681201865X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1598

doi:10.1107/S160053681201865X

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2-Chloro-4-(3,3-dichloroallyloxy)-1-nitrobenzene

Xiao-feng Yu,^a ^* Zheng-jun Xia ^b and Chun-ya Li ^b

^aSchool of Pharmaceutics, Jiangsu University, Zhenjiang 212013, People's Republic of China, and ^bR&D Center, Jiangsu Yabang Pharmaceutical Group, Liangchang Road East No. 6 Jingtan, Changzhou 213200, People's Republic of China
^*Correspondence e-mail: zhengfyu@126.com

(Received 2 April 2012; accepted 25 April 2012; online 2 May 2012)

In the crystal structure of the title compound, C₉H₆Cl₃NO₃, molecules are connected by C—H⋯O hydrogen bonds, forming chains along the b axis. The dihedral angle between the benzene ring and the plane of the nitro group is 16.2 (1)° and that between the benzene ring and the plane of the dichloroallyl group is 10.2 (1)°.

Related literature

For background to the applications of the title compound, see: Kolosov et al. (2002 ). For the synthesis, see: Walker et al. (2005 ).

Experimental

Crystal data

C₉H₆Cl₃NO₃
M_r = 282.50
Monoclinic, P 2₁ /c
a = 12.476 (3) Å
b = 12.775 (3) Å
c = 7.2230 (14) Å
β = 92.32 (3)°
V = 1150.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.799, T_max = 0.926
2300 measured reflections
2118 independent reflections
1414 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.183
S = 1.00
2118 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O3ⁱ	0.93	2.54	3.449 (7)	165
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXS97 (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/S160053681201865X/vm2169sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201865X/vm2169Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201865X/vm2169Isup3.cml

checkCIF report

Comment top

The title compound is an important intermediate in the synthesis of phenanthrenes, which can be utilized to synthesize organic semiconductors and conjugated polymers (Walker et al., 2005). These materials are of wide current interest for applications in electronic and optoelectronic devices including light-emitting diodes (Kolosov et al., 2002). We report here the crystal structure of the title compound, (I), which is of interest to us in this field.

The molecular structure of (I) is shown in Fig. 1. There is an intermolecular contact C—H···O in the title compound, forming molecular chains along the b axis direction (Table 1, Fig. 2). These molecular chains are linked by weak π—π interactions (Cg1···Cg1ⁱdistance = 3.724 (3) Å, Cg1 is the centroid of ring C1-C6, symmetry code: (i) x, 5/2 - y, -1/2 + z) to give a three-dimensional network, which seems to be very effective in the stabilization of the crystal structure.

The dihedral angles between the planes A (atoms C1—C6), B (atoms N/O2/O3), C (atoms C7/C8/H8A/C9/Cl2/Cl3) are: A/B = 16.2 (1)°, A/C = 10.2 (1)°.

Related literature top

For background to the applications of the title compound, see: Kolosov et al. (2002). For the synthesis, see: Walker et al. (2005).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Walker et al., 2005). The 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: SHELXS97 (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.
	Fig. 2. A packing diagram of (I) viewed along the a axis (C-H···O hydrogen bonds are shown as broken lines).

2-Chloro-4-(3,3-dichloroallyloxy)-1-nitrobenzene top

Crystal data top

C₉H₆Cl₃NO₃	F(000) = 568
M_r = 282.50	D_x = 1.631 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.476 (3) Å	θ = 10–13°
b = 12.775 (3) Å	µ = 0.79 mm⁻¹
c = 7.2230 (14) Å	T = 293 K
β = 92.32 (3)°	Block, colourless
V = 1150.3 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1414 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.4°, θ_min = 1.6°
ω/2θ scans	h = −15→15
Absorption correction: ψ scan (North et al., 1968)	k = −15→0
T_min = 0.799, T_max = 0.926	l = 0→8
2300 measured reflections	3 standard reflections every 200 reflections
2118 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.7P] where P = (F_o² + 2F_c²)/3
2118 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₉H₆Cl₃NO₃	V = 1150.3 (4) Å³
M_r = 282.50	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.476 (3) Å	µ = 0.79 mm⁻¹
b = 12.775 (3) Å	T = 293 K
c = 7.2230 (14) Å	0.30 × 0.20 × 0.10 mm
β = 92.32 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1414 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.023
T_min = 0.799, T_max = 0.926	3 standard reflections every 200 reflections
2300 measured reflections	intensity decay: 1%
2118 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.183	H-atom parameters constrained
S = 1.00	Δρ_max = 0.52 e Å⁻³
2118 reflections	Δρ_min = −0.42 e Å⁻³
145 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
N	0.0625 (4)	1.3968 (3)	0.1971 (7)	0.0603 (12)
Cl1	0.31002 (11)	1.42882 (9)	0.1250 (2)	0.0643 (4)
C1	0.2996 (4)	1.2216 (4)	0.1245 (7)	0.0468 (11)
H1A	0.3724	1.2256	0.1021	0.056*
O1	0.3184 (3)	1.0417 (2)	0.1211 (5)	0.0560 (9)
Cl2	0.45065 (11)	0.67097 (10)	0.1106 (2)	0.0685 (5)
C2	0.2415 (4)	1.3117 (3)	0.1436 (7)	0.0452 (11)
O2	0.1009 (4)	1.4802 (3)	0.2323 (8)	0.1053 (18)
Cl3	0.22239 (11)	0.70364 (10)	0.1046 (2)	0.0679 (5)
C3	0.1325 (3)	1.3051 (3)	0.1756 (7)	0.0441 (11)
O3	−0.0309 (3)	1.3841 (4)	0.1923 (12)	0.157 (3)
C4	0.0837 (4)	1.2084 (4)	0.1880 (7)	0.0505 (12)
H4A	0.0105	1.2044	0.2073	0.061*
C5	0.1433 (4)	1.1170 (4)	0.1718 (7)	0.0496 (12)
H5A	0.1106	1.0520	0.1837	0.060*
C6	0.2501 (4)	1.1231 (3)	0.1384 (6)	0.0432 (11)
C7	0.2718 (4)	0.9380 (3)	0.1296 (8)	0.0585 (14)
H7A	0.2213	0.9272	0.0256	0.070*
H7B	0.2340	0.9297	0.2434	0.070*
C8	0.3611 (4)	0.8612 (4)	0.1230 (7)	0.0542 (13)
H8A	0.4310	0.8865	0.1258	0.065*
C9	0.3467 (4)	0.7601 (4)	0.1137 (7)	0.0493 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.055 (3)	0.040 (2)	0.087 (3)	0.0090 (19)	0.005 (2)	−0.007 (2)
Cl1	0.0614 (8)	0.0331 (6)	0.0991 (11)	−0.0085 (5)	0.0112 (7)	−0.0018 (6)
C1	0.042 (2)	0.037 (2)	0.062 (3)	0.0005 (19)	0.013 (2)	0.005 (2)
O1	0.0505 (18)	0.0324 (16)	0.086 (2)	−0.0030 (14)	0.0182 (17)	0.0000 (17)
Cl2	0.0583 (8)	0.0419 (7)	0.1055 (12)	0.0096 (6)	0.0065 (7)	−0.0031 (7)
C2	0.052 (3)	0.026 (2)	0.058 (3)	−0.0048 (19)	0.005 (2)	−0.001 (2)
O2	0.081 (3)	0.042 (2)	0.194 (6)	0.011 (2)	0.022 (3)	−0.013 (3)
Cl3	0.0563 (8)	0.0419 (7)	0.1063 (12)	−0.0047 (6)	0.0121 (7)	−0.0094 (7)
C3	0.044 (2)	0.031 (2)	0.058 (3)	0.0050 (19)	0.002 (2)	0.000 (2)
O3	0.037 (2)	0.069 (3)	0.366 (10)	0.009 (2)	0.019 (4)	−0.050 (5)
C4	0.041 (2)	0.046 (3)	0.065 (3)	−0.004 (2)	0.010 (2)	−0.001 (2)
C5	0.054 (3)	0.030 (2)	0.066 (3)	−0.005 (2)	0.011 (2)	0.003 (2)
C6	0.051 (3)	0.029 (2)	0.050 (3)	0.0001 (19)	0.010 (2)	0.001 (2)
C7	0.048 (3)	0.032 (2)	0.096 (4)	−0.006 (2)	0.010 (3)	−0.002 (3)
C8	0.052 (3)	0.037 (3)	0.074 (3)	−0.005 (2)	0.006 (2)	−0.002 (2)
C9	0.052 (3)	0.037 (3)	0.059 (3)	0.004 (2)	0.008 (2)	0.006 (2)

Geometric parameters (Å, º) top

N—O3	1.176 (6)	Cl3—C9	1.709 (5)
N—O2	1.192 (6)	C3—C4	1.382 (6)
N—C3	1.472 (6)	C4—C5	1.392 (6)
Cl1—C2	1.731 (4)	C4—H4A	0.9300
C1—C2	1.370 (6)	C5—C6	1.367 (6)
C1—C6	1.406 (6)	C5—H5A	0.9300
C1—H1A	0.9300	C7—C8	1.487 (6)
O1—C6	1.353 (5)	C7—H7A	0.9700
O1—C7	1.449 (5)	C7—H7B	0.9700
Cl2—C9	1.727 (5)	C8—C9	1.304 (7)
C2—C3	1.392 (6)	C8—H8A	0.9300

O3—N—O2	121.2 (5)	C6—C5—H5A	120.2
O3—N—C3	118.6 (4)	C4—C5—H5A	120.2
O2—N—C3	119.9 (4)	O1—C6—C5	126.4 (4)
C2—C1—C6	120.6 (4)	O1—C6—C1	113.6 (4)
C2—C1—H1A	119.7	C5—C6—C1	119.9 (4)
C6—C1—H1A	119.7	O1—C7—C8	107.5 (4)
C6—O1—C7	116.4 (4)	O1—C7—H7A	110.2
C1—C2—C3	119.4 (4)	C8—C7—H7A	110.2
C1—C2—Cl1	117.0 (4)	O1—C7—H7B	110.2
C3—C2—Cl1	123.6 (3)	C8—C7—H7B	110.2
C4—C3—C2	120.1 (4)	H7A—C7—H7B	108.5
C4—C3—N	116.1 (4)	C9—C8—C7	123.6 (5)
C2—C3—N	123.9 (4)	C9—C8—H8A	118.2
C3—C4—C5	120.4 (4)	C7—C8—H8A	118.2
C3—C4—H4A	119.8	C8—C9—Cl3	122.9 (4)
C5—C4—H4A	119.8	C8—C9—Cl2	123.4 (4)
C6—C5—C4	119.7 (4)	Cl3—C9—Cl2	113.7 (3)

C6—C1—C2—C3	−0.5 (7)	C3—C4—C5—C6	−1.8 (7)
C6—C1—C2—Cl1	179.8 (4)	C7—O1—C6—C5	3.3 (7)
C1—C2—C3—C4	0.0 (7)	C7—O1—C6—C1	−178.5 (4)
Cl1—C2—C3—C4	179.8 (4)	C4—C5—C6—O1	179.4 (5)
C1—C2—C3—N	−179.6 (5)	C4—C5—C6—C1	1.3 (7)
Cl1—C2—C3—N	0.1 (7)	C2—C1—C6—O1	−178.4 (4)
O3—N—C3—C4	−12.3 (8)	C2—C1—C6—C5	−0.2 (7)
O2—N—C3—C4	162.1 (5)	C6—O1—C7—C8	−175.5 (4)
O3—N—C3—C2	167.3 (6)	O1—C7—C8—C9	−174.5 (5)
O2—N—C3—C2	−18.2 (8)	C7—C8—C9—Cl3	0.9 (8)
C2—C3—C4—C5	1.1 (7)	C7—C8—C9—Cl2	−178.7 (4)
N—C3—C4—C5	−179.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O3ⁱ	0.93	2.54	3.449 (7)	165

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₆Cl₃NO₃
M_r	282.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.476 (3), 12.775 (3), 7.2230 (14)
β (°)	92.32 (3)
V (Å³)	1150.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.799, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	2300, 2118, 1414
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.183, 1.00
No. of reflections	2118
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.42

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O3ⁱ	0.9300	2.5400	3.449 (7)	165.00

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

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