1-(3,3-Dichloro­all­yloxy)-2-nitro­benzene

Ren, D.; Wang, Y.

doi:10.1107/S1600536812010070

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1049

doi:10.1107/S1600536812010070

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1-(3,3-Dichloroallyloxy)-2-nitrobenzene

Dong-mei Ren ^a ^* and Yong-yi Wang ^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 3 March 2012; accepted 7 March 2012; online 14 March 2012)

In the title compound, C₉H₇Cl₂NO₃, the dihedral angle between the benzene ring and the plane of the nitro group is 50.2 (1)°, and that between the benzene ring and the best plane through the dichloroallyl fragment is 40.1 (1)°.

Related literature

For the synthesis and applications of the title compound, see: Walker et al. (2005 ). For bond-length data, see: Allen et al. (1987).

Experimental

Crystal data

C₉H₇Cl₂NO₃
M_r = 248.06
Monoclinic, P 2₁ /c
a = 4.0210 (8) Å
b = 21.506 (4) Å
c = 12.333 (3) Å
β = 96.41 (3)°
V = 1059.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.60 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 = 0.841, T_max = 0.943
4390 measured reflections
1941 independent reflections
1416 reflections with I > 2σ(I)
R_int = 0.063
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.164
S = 1.00
1941 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.29 e Å⁻³

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/S1600536812010070/vm2161sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010070/vm2161Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812010070/vm2161Isup3.cml

checkCIF report

Comment top

The title compound, 1-(3,3-dichloroallyloxy)-2-nitrobenzene is an important intermediate in the synthesis of phenanthrenes (Walker et al., 2005). Here we report here the molecular and crystal structure of the title compound (Fig. 1).

There are no classic hydrogen bonds found, but a short intramolecular contact C7—H7B···Cl2 is observed (C7—H7B: 0.97 Å, H7B···Cl2: 2.700 Å, C7···Cl2: 3.139 (3) Å, C7—H7B···Cl2: 108.00).

The dihedral angle between the benzene ring (C1—C6) and the plane of the nitro group is 50.2 (1)°, and between the benzene ring and the best plane through the dichloroallyl fragment (C7—C9, Cl1, Cl2) 40.1 (1)°.

The packing is shown in Figure 2 and contains a short Cl1···Cl2 (x + 1, y, z) contact (3.6668 (16) Å).

Related literature top

For the synthesis and applications of the title compound, see: Walker et al. (2005). For bond-length data, see: Allen et al. (1987).

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.

Structure description top

The packing is shown in Figure 2 and contains a short Cl1···Cl2 (x + 1, y, z) contact (3.6668 (16) Å).

For the synthesis and applications of the title compound, see: Walker et al. (2005). For bond-length data, see: Allen et al. (1987).

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. Packing diagram of (I) viewed down the a-axis.

1-(3,3-Dichloroallyloxy)-2-nitrobenzene top

Crystal data top

C₉H₇Cl₂NO₃	F(000) = 504
M_r = 248.06	D_x = 1.555 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 4.0210 (8) Å	θ = 10–13°
b = 21.506 (4) Å	µ = 0.60 mm⁻¹
c = 12.333 (3) Å	T = 293 K
β = 96.41 (3)°	Block, colourless
V = 1059.8 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1416 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.063
Graphite monochromator	θ_max = 25.4°, θ_min = 1.9°
ω/2θ scans	h = 0→4
Absorption correction: ψ scan (North et al., 1968)	k = −25→25
T_min = 0.841, T_max = 0.943	l = −14→14
4390 measured reflections	3 standard reflections every 200 reflections
1941 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.2P] where P = (F_o² + 2F_c²)/3
1941 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₉H₇Cl₂NO₃	V = 1059.8 (4) Å³
M_r = 248.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.0210 (8) Å	µ = 0.60 mm⁻¹
b = 21.506 (4) Å	T = 293 K
c = 12.333 (3) Å	0.30 × 0.20 × 0.10 mm
β = 96.41 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1416 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.063
T_min = 0.841, T_max = 0.943	3 standard reflections every 200 reflections
4390 measured reflections	intensity decay: 1%
1941 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.164	H-atom parameters constrained
S = 1.00	Δρ_max = 0.36 e Å⁻³
1941 reflections	Δρ_min = −0.29 e Å⁻³
136 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	−0.0930 (8)	0.17453 (13)	0.1420 (2)	0.0607 (7)
Cl1	0.6644 (2)	0.46194 (4)	0.18851 (7)	0.0679 (3)
C1	0.1777 (8)	0.19522 (14)	0.4390 (2)	0.0509 (7)
H1A	0.2853	0.2241	0.4870	0.061*
O1	−0.0106 (14)	0.13642 (18)	0.0804 (2)	0.1309 (16)
Cl2	0.3945 (3)	0.44863 (4)	0.39369 (7)	0.0729 (3)
C2	0.0679 (9)	0.13945 (15)	0.4779 (3)	0.0591 (8)
H2A	0.0987	0.1315	0.5525	0.071*
O2	−0.2241 (10)	0.22293 (15)	0.1110 (2)	0.0977 (10)
O3	0.2229 (6)	0.26084 (9)	0.28095 (15)	0.0551 (6)
C3	−0.0868 (9)	0.09520 (15)	0.4083 (3)	0.0612 (9)
H3A	−0.1589	0.0579	0.4358	0.073*
C4	−0.1329 (9)	0.10674 (14)	0.2985 (3)	0.0568 (8)
H4A	−0.2332	0.0771	0.2507	0.068*
C5	−0.0295 (8)	0.16271 (13)	0.2596 (2)	0.0469 (7)
C6	0.1265 (7)	0.20796 (12)	0.3279 (2)	0.0430 (6)
C7	0.4163 (8)	0.30524 (12)	0.3477 (2)	0.0480 (7)
H7A	0.6064	0.2853	0.3891	0.058*
H7B	0.2808	0.3250	0.3982	0.058*
C8	0.5296 (7)	0.35136 (14)	0.2706 (2)	0.0491 (7)
H8A	0.6086	0.3361	0.2077	0.059*
C9	0.5280 (8)	0.41198 (13)	0.2834 (2)	0.0495 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0812 (19)	0.0533 (16)	0.0480 (13)	−0.0130 (14)	0.0079 (14)	−0.0101 (12)
Cl1	0.0832 (6)	0.0472 (5)	0.0752 (6)	−0.0049 (4)	0.0172 (5)	0.0102 (4)
C1	0.0600 (18)	0.0462 (16)	0.0462 (14)	0.0020 (13)	0.0041 (14)	−0.0025 (11)
O1	0.220 (5)	0.112 (3)	0.0666 (17)	0.022 (3)	0.040 (2)	−0.0235 (17)
Cl2	0.1011 (7)	0.0526 (5)	0.0672 (5)	0.0023 (4)	0.0188 (5)	−0.0173 (4)
C2	0.074 (2)	0.0536 (18)	0.0500 (16)	0.0020 (16)	0.0084 (16)	0.0078 (13)
O2	0.135 (3)	0.095 (2)	0.0579 (15)	0.003 (2)	−0.0152 (16)	0.0072 (14)
O3	0.0769 (15)	0.0431 (11)	0.0442 (10)	−0.0160 (10)	0.0011 (10)	0.0008 (8)
C3	0.079 (2)	0.0393 (16)	0.0656 (19)	−0.0027 (15)	0.0118 (17)	0.0086 (13)
C4	0.067 (2)	0.0393 (15)	0.0654 (19)	−0.0041 (14)	0.0134 (16)	−0.0075 (13)
C5	0.0562 (17)	0.0428 (16)	0.0429 (13)	0.0000 (12)	0.0112 (12)	−0.0062 (11)
C6	0.0482 (15)	0.0364 (14)	0.0451 (13)	0.0027 (11)	0.0082 (12)	−0.0041 (10)
C7	0.0560 (17)	0.0402 (15)	0.0464 (14)	−0.0034 (12)	−0.0003 (13)	−0.0040 (11)
C8	0.0521 (17)	0.0419 (15)	0.0537 (15)	−0.0033 (12)	0.0078 (14)	−0.0035 (11)
C9	0.0548 (18)	0.0421 (16)	0.0512 (16)	−0.0006 (12)	0.0042 (14)	−0.0020 (11)

Geometric parameters (Å, º) top

N—O1	1.189 (4)	O3—C7	1.432 (3)
N—O2	1.209 (4)	C3—C4	1.368 (5)
N—C5	1.466 (4)	C3—H3A	0.9300
Cl1—C9	1.723 (3)	C4—C5	1.378 (4)
C1—C2	1.382 (4)	C4—H4A	0.9300
C1—C6	1.390 (4)	C5—C6	1.390 (4)
C1—H1A	0.9300	C7—C8	1.481 (4)
Cl2—C9	1.710 (3)	C7—H7A	0.9700
C2—C3	1.382 (5)	C7—H7B	0.9700
C2—H2A	0.9300	C8—C9	1.313 (4)
O3—C6	1.352 (3)	C8—H8A	0.9300

O1—N—O2	122.3 (3)	C4—C5—N	118.1 (3)
O1—N—C5	118.8 (3)	C6—C5—N	119.7 (3)
O2—N—C5	118.9 (3)	O3—C6—C1	124.7 (2)
C2—C1—C6	119.7 (3)	O3—C6—C5	117.4 (2)
C2—C1—H1A	120.1	C1—C6—C5	117.8 (3)
C6—C1—H1A	120.1	O3—C7—C8	105.3 (2)
C1—C2—C3	121.4 (3)	O3—C7—H7A	110.7
C1—C2—H2A	119.3	C8—C7—H7A	110.7
C3—C2—H2A	119.3	O3—C7—H7B	110.7
C6—O3—C7	118.5 (2)	C8—C7—H7B	110.7
C4—C3—C2	119.5 (3)	H7A—C7—H7B	108.8
C4—C3—H3A	120.3	C9—C8—C7	125.6 (3)
C2—C3—H3A	120.3	C9—C8—H8A	117.2
C3—C4—C5	119.4 (3)	C7—C8—H8A	117.2
C3—C4—H4A	120.3	C8—C9—Cl2	124.0 (2)
C5—C4—H4A	120.3	C8—C9—Cl1	122.1 (2)
C4—C5—C6	122.2 (3)	Cl2—C9—Cl1	113.89 (17)

C6—C1—C2—C3	1.3 (5)	C2—C1—C6—O3	180.0 (3)
C1—C2—C3—C4	−0.1 (6)	C2—C1—C6—C5	−1.3 (4)
C2—C3—C4—C5	−1.1 (5)	C4—C5—C6—O3	178.9 (3)
C3—C4—C5—C6	1.1 (5)	N—C5—C6—O3	−2.1 (4)
C3—C4—C5—N	−177.9 (3)	C4—C5—C6—C1	0.1 (4)
O1—N—C5—C4	−50.7 (5)	N—C5—C6—C1	179.1 (3)
O2—N—C5—C4	130.1 (4)	C6—O3—C7—C8	170.5 (2)
O1—N—C5—C6	130.2 (4)	O3—C7—C8—C9	136.4 (3)
O2—N—C5—C6	−49.0 (5)	C7—C8—C9—Cl2	0.4 (5)
C7—O3—C6—C1	5.5 (4)	C7—C8—C9—Cl1	−179.8 (2)
C7—O3—C6—C5	−173.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···Cl2	0.97	2.70	3.139 (3)	108

Experimental details

Crystal data
Chemical formula	C₉H₇Cl₂NO₃
M_r	248.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.0210 (8), 21.506 (4), 12.333 (3)
β (°)	96.41 (3)
V (Å³)	1059.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.841, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	4390, 1941, 1416
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.164, 1.00
No. of reflections	1941
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.29

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
C7—H7B···Cl2	0.97	2.70	3.139 (3)	108

Acknowledgements

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

References

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