2-Chloro-4-(3,3-dichloro-all-yloxy)-1-nitro-benzene.

Abstract

In the crystal structure of the title compound, C(9)H(6)Cl(3)NO(3), mol-ecules 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 dichloro-allyl group is 10.2 (1)°.

Full text

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2-Chloro-4-(3,3-dichloroallyloxy)-1-
nitrobenzene
Xiao-feng Yu,a* Zheng-jun Xiaband Chun-ya Lib
aSchool of Pharmaceutics, Jiangsu University, Zhenjiang 212013, People’s Republic
of China, andbR&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
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.007 A ˚;
R factor = 0.066; wR factor = 0.183; data-to-parameter ratio = 14.6.
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
Mr= 282.50
Monoclinic, P21=c
a = 12.476 (3) A˚
b = 12.775 (3) A˚
c = 7.2230 (14) A˚
? = 92.32 (3)?
V = 1150.3 (4) A˚3
Z = 4
Mo K? radiation
? = 0.79 mm?1
T = 293 K
0.30 ? 0.20 ? 0.10 mm
Data collection
Enraf–Nonius CAD-4
diffractometer
Absorption correction: scan
(North et al., 1968)
Tmin= 0.799, Tmax= 0.926
2300 measured reflections
2118 independent reflections
1414 reflections with I > 2?(I)
Rint= 0.023
3 standard reflections every 200
reflections
intensity decay: 1%
Refinement
R[F2> 2?(F2)] = 0.066
wR(F2) = 0.183
S = 1.00
2118 reflections
145 parameters
H-atom parameters constrained
??max= 0.52 e A˚?3
??min= ?0.42 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
C5—H5A???O3i
Symmetry code: (i) ?x;y ?1
D—HH???AD???AD—H???A
0.93 2.543.449 (7) 165
2;?z þ1
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.
The authors thank the Center of Testing and Analysis,
Nanjing University, for the data collection.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: VM2169).
References
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Nether-
lands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
Kolosov, S., Adamovich, V., Djurovich, P., Thompson, M. E. & Adachi, C.
(2002). J. Am. Chem. Soc. 124, 9945–9954.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–
359.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Walker, E. R., Leung, S. Y. & Barrett, A. G. M. (2005). Tetrahedron Lett. 46,
6537–6540.
organic compounds
o1598
Yu et al.
doi:10.1107/S160053681201865X
Acta Cryst. (2012). E68, o1598
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials
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Acta Cryst. (2012). E68, o1598
supplementary materials
Acta Cryst. (2012). E68, o1598 [doi:10.1107/S160053681201865X]
2-Chloro-4-(3,3-dichloroallyloxy)-1-nitrobenzene
Xiao-feng Yu, Zheng-jun Xia and Chun-ya Li
Comment
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···Cg1i distance = 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)°.
Experimental
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.
Refinement
All H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.93 Å for
aromatic H and 0.96 Å for alkyl H, respectively. The Uiso(H) = xUeq(C), where x = 1.2 for aromatic H and x = 1.5 for other
H.
Computing details
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).

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Acta Cryst. (2012). E68, o1598
Figure 1
The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level.
Figure 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
Crystal data
C9H6Cl3NO3
Mr = 282.50
Monoclinic, P21/c
Hall symbol: -P 2ybc
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
F(000) = 568
Dx = 1.631 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 25 reflections
θ = 10–13°
µ = 0.79 mm−1

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Acta Cryst. (2012). E68, o1598
T = 293 K
Block, colourless
0.30 × 0.20 × 0.10 mm
Data collection
Enraf–Nonius CAD-4
diffractometer
Radiation source: fine-focus sealed tube
Graphite monochromator
ω/2θ scans
Absorption correction: ψ scan
(North et al., 1968)
Tmin = 0.799, Tmax = 0.926
2300 measured reflections
2118 independent reflections
1414 reflections with I > 2σ(I)
Rint = 0.023
θmax = 25.4°, θmin = 1.6°
h = −15→15
k = −15→0
l = 0→8
3 standard reflections every 200 reflections
intensity decay: 1%
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.066
wR(F2) = 0.183
S = 1.00
2118 reflections
145 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.1P)2 + 0.7P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.52 e Å−3
Δρmin = −0.42 e Å−3
Special details
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)
xyzUiso*/Ueq
N
Cl1
C1
H1A
O1
Cl2
C2
O2
Cl3
C3
O3
C4
H4A
C5
0.0625 (4)
0.31002 (11)
0.2996 (4)
0.3724
0.3184 (3)
0.45065 (11)
0.2415 (4)
0.1009 (4)
0.22239 (11)
0.1325 (3)
−0.0309 (3)
0.0837 (4)
0.0105
0.1433 (4)
1.3968 (3)
1.42882 (9)
1.2216 (4)
1.2256
1.0417 (2)
0.67097 (10)
1.3117 (3)
1.4802 (3)
0.70364 (10)
1.3051 (3)
1.3841 (4)
1.2084 (4)
1.2044
1.1170 (4)
0.1971 (7)
0.1250 (2)
0.1245 (7)
0.1021
0.1211 (5)
0.1106 (2)
0.1436 (7)
0.2323 (8)
0.1046 (2)
0.1756 (7)
0.1923 (12)
0.1880 (7)
0.2073
0.1718 (7)
0.0603 (12)
0.0643 (4)
0.0468 (11)
0.056*
0.0560 (9)
0.0685 (5)
0.0452 (11)
0.1053 (18)
0.0679 (5)
0.0441 (11)
0.157 (3)
0.0505 (12)
0.061*
0.0496 (12)

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Acta Cryst. (2012). E68, o1598
H5A
C6
C7
H7A
H7B
C8
H8A
C9
0.1106
0.2501 (4)
0.2718 (4)
0.2213
0.2340
0.3611 (4)
0.4310
0.3467 (4)
1.0520
1.1231 (3)
0.9380 (3)
0.9272
0.9297
0.8612 (4)
0.8865
0.7601 (4)
0.1837
0.1384 (6)
0.1296 (8)
0.0256
0.2434
0.1230 (7)
0.1258
0.1137 (7)
0.060*
0.0432 (11)
0.0585 (14)
0.070*
0.070*
0.0542 (13)
0.065*
0.0493 (12)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N
Cl1
C1
O1
Cl2
C2
O2
Cl3
C3
O3
C4
C5
C6
C7
C8
C9
0.055 (3)
0.0614 (8)
0.042 (2)
0.0505 (18)
0.0583 (8)
0.052 (3)
0.081 (3)
0.0563 (8)
0.044 (2)
0.037 (2)
0.041 (2)
0.054 (3)
0.051 (3)
0.048 (3)
0.052 (3)
0.052 (3)
0.040 (2)
0.0331 (6)
0.037 (2)
0.0324 (16)
0.0419 (7)
0.026 (2)
0.042 (2)
0.0419 (7)
0.031 (2)
0.069 (3)
0.046 (3)
0.030 (2)
0.029 (2)
0.032 (2)
0.037 (3)
0.037 (3)
0.087 (3)
0.0991 (11)
0.062 (3)
0.086 (2)
0.1055 (12)
0.058 (3)
0.194 (6)
0.1063 (12)
0.058 (3)
0.366 (10)
0.065 (3)
0.066 (3)
0.050 (3)
0.096 (4)
0.074 (3)
0.059 (3)
0.0090 (19)
−0.0085 (5)
0.0005 (19)
−0.0030 (14)
0.0096 (6)
−0.0048 (19)
0.011 (2)
−0.0047 (6)
0.0050 (19)
0.009 (2)
−0.004 (2)
−0.005 (2)
0.0001 (19)
−0.006 (2)
−0.005 (2)
0.004 (2)
0.005 (2)
0.0112 (7)
0.013 (2)
0.0182 (17)
0.0065 (7)
0.005 (2)
0.022 (3)
0.0121 (7)
0.002 (2)
0.019 (4)
0.010 (2)
0.011 (2)
0.010 (2)
0.010 (3)
0.006 (2)
0.008 (2)
−0.007 (2)
−0.0018 (6)
0.005 (2)
0.0000 (17)
−0.0031 (7)
−0.001 (2)
−0.013 (3)
−0.0094 (7)
0.000 (2)
−0.050 (5)
−0.001 (2)
0.003 (2)
0.001 (2)
−0.002 (3)
−0.002 (2)
0.006 (2)
Geometric parameters (Å, º)
N—O3
N—O2
N—C3
Cl1—C2
C1—C2
C1—C6
C1—H1A
O1—C6
O1—C7
Cl2—C9
C2—C3
1.176 (6)
1.192 (6)
1.472 (6)
1.731 (4)
1.370 (6)
1.406 (6)
0.9300
1.353 (5)
1.449 (5)
1.727 (5)
1.392 (6)
Cl3—C9
C3—C4
C4—C5
C4—H4A
C5—C6
C5—H5A
C7—C8
C7—H7A
C7—H7B
C8—C9
C8—H8A
1.709 (5)
1.382 (6)
1.392 (6)
0.9300
1.367 (6)
0.9300
1.487 (6)
0.9700
0.9700
1.304 (7)
0.9300
O3—N—O2
O3—N—C3
O2—N—C3
C2—C1—C6
C2—C1—H1A
C6—C1—H1A
C6—O1—C7
121.2 (5)
118.6 (4)
119.9 (4)
120.6 (4)
119.7
119.7
116.4 (4)
C6—C5—H5A
C4—C5—H5A
O1—C6—C5
O1—C6—C1
C5—C6—C1
O1—C7—C8
O1—C7—H7A
120.2
120.2
126.4 (4)
113.6 (4)
119.9 (4)
107.5 (4)
110.2