1-(3,3-Dichloro­all­yloxy)-4-methyl-2-nitro­benzene

Ren, D.

doi:10.1107/S1600536812023057

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1929

doi:10.1107/S1600536812023057

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1-(3,3-Dichloroallyloxy)-4-methyl-2-nitrobenzene

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 2 May 2012; accepted 20 May 2012; online 31 May 2012)

In the title compound, C₁₀H₉Cl₂NO₃, the dihedral angle between the benzene ring and the plane of the nitro group is 39.1 (1)°, while that between the benzene ring and the plane through the three C and two Cl atoms of the dichloroallyloxy unit is 40.1 (1)°. In the crystal, C—H⋯O hydrogen bonds to the nitro groups form chains along the b axis. These chains are linked by inversion-related pairs of Cl⋯O interactions at a distance of 3.060 (3) Å, forming sheets approximately parallel to [-201] and generating R₂²(18) rings. π–π contacts between benzene rings in adjacent sheets, with centroid–centroid distances of 3.671 (2) Å, stack molecules along c.

Related literature

For background to the applications of the title compound, see: Kolosov et al. (2002 ). For its synthesis, see: Walker et al. (2005 ). For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₉Cl₂NO₃
M_r = 262.08
Triclinic, $[P \overline 1]$
a = 7.5430 (15) Å
b = 7.7630 (16) Å
c = 10.713 (2) Å
α = 83.69 (3)°
β = 88.78 (3)°
γ = 67.23 (3)°
V = 574.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.56 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 = 0.851, T_max = 0.947
2277 measured reflections
2103 independent reflections
1638 reflections with I > 2σ(I)
R_int = 0.021
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.156
S = 1.01
2103 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2ⁱ	0.93	2.59	3.241 (4)	127
Symmetry code: (i) x, y+1, z.

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/S1600536812023057/sj5235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023057/sj5235Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023057/sj5235Isup3.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 with 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), as we have interests in this field.

The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the (C1···C6) rings and the (C8/C9/C10/Cl1/Cl2/H9A) segment of the alloyloxy substituent is 40.1 (1)° with the nitro group (N/O1/O2) inclined at 39.1 (1)° to the ring plane. Bond distances in the molecule are normal (Allen et al. 1987).

In the crystal structure there is an intermolecular C1—H1A···O2 hydrogen bond that links molecules into chains along the b axis (Table 1, Fig. 2). Short Cl1···O1ⁱ (ⁱ = 1-x, -y, 1-z) contacts at a distance of 3.060 (3) Å form inversion dimers and generate R²₂(18) rings (Bernstein et al., 1995). These contacts link the hydrogen bonded chains into sheets approximately parallel to [-2 0 1]. Additional π···π contacts with centroid to centroid distances 3.671 (2) Å between benzene rings in adjacent sheets, stack molecules along c and generate a three dimensional network structure.

Related literature top

For background to the applications of the title compound, see: Kolosov et al. (2002). For its synthesis, see: Walker et al. (2005). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995).

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: 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.
	Fig. 2. A packing diagram of (I).

1-(3,3-Dichloroallyloxy)-4-methyl-2-nitrobenzene top

Crystal data top

C₁₀H₉Cl₂NO₃	Z = 2
M_r = 262.08	F(000) = 268
Triclinic, P1	D_x = 1.514 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5430 (15) Å	Cell parameters from 25 reflections
b = 7.7630 (16) Å	θ = 10–13°
c = 10.713 (2) Å	µ = 0.56 mm⁻¹
α = 83.69 (3)°	T = 293 K
β = 88.78 (3)°	Block, colourless
γ = 67.23 (3)°	0.30 × 0.20 × 0.10 mm
V = 574.8 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1638 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.4°, θ_min = 1.9°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −8→9
T_min = 0.851, T_max = 0.947	l = −12→12
2277 measured reflections	3 standard reflections every 200 reflections
2103 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.130P] where P = (F_o² + 2F_c²)/3
2103 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₀H₉Cl₂NO₃	γ = 67.23 (3)°
M_r = 262.08	V = 574.8 (2) Å³
Triclinic, P1	Z = 2
a = 7.5430 (15) Å	Mo Kα radiation
b = 7.7630 (16) Å	µ = 0.56 mm⁻¹
c = 10.713 (2) Å	T = 293 K
α = 83.69 (3)°	0.30 × 0.20 × 0.10 mm
β = 88.78 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1638 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.021
T_min = 0.851, T_max = 0.947	3 standard reflections every 200 reflections
2277 measured reflections	intensity decay: 1%
2103 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.01	Δρ_max = 0.28 e Å⁻³
2103 reflections	Δρ_min = −0.28 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
Cl1	0.35049 (14)	0.31042 (13)	0.40617 (7)	0.0723 (3)
Cl2	0.20254 (13)	0.53282 (12)	0.60994 (8)	0.0713 (3)
O1	0.8637 (4)	−0.2999 (3)	0.8304 (2)	0.0767 (8)
O2	0.7766 (4)	−0.4263 (3)	0.9976 (2)	0.0731 (7)
O3	0.6554 (3)	0.0677 (3)	0.82149 (17)	0.0542 (5)
N	0.8110 (4)	−0.2976 (3)	0.9385 (2)	0.0534 (6)
C1	0.6985 (4)	0.1898 (4)	1.0130 (3)	0.0506 (7)
H1A	0.6478	0.3133	0.9755	0.061*
C2	0.7574 (4)	0.1533 (4)	1.1372 (3)	0.0511 (7)
H2A	0.7446	0.2537	1.1816	0.061*
C3	0.8352 (4)	−0.0276 (4)	1.1987 (2)	0.0461 (6)
C4	0.8481 (4)	−0.1727 (4)	1.1298 (2)	0.0457 (6)
H4A	0.8972	−0.2958	1.1681	0.055*
C5	0.7892 (4)	−0.1372 (4)	1.0055 (2)	0.0411 (6)
C6	0.7139 (4)	0.0451 (4)	0.9434 (2)	0.0417 (6)
C7	0.9018 (5)	−0.0623 (5)	1.3344 (3)	0.0661 (9)
H7A	0.8808	0.0554	1.3652	0.099*
H7B	1.0364	−0.1409	1.3409	0.099*
H7C	0.8306	−0.1235	1.3835	0.099*
C8	0.5768 (5)	0.2544 (4)	0.7592 (3)	0.0515 (7)
H8A	0.6681	0.3142	0.7612	0.062*
H8B	0.4597	0.3296	0.7989	0.062*
C9	0.5358 (5)	0.2340 (4)	0.6279 (3)	0.0537 (7)
H9A	0.6257	0.1337	0.5915	0.064*
C10	0.3856 (5)	0.3433 (4)	0.5586 (3)	0.0517 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0946 (7)	0.0785 (6)	0.0430 (4)	−0.0320 (5)	−0.0101 (4)	−0.0062 (4)
Cl2	0.0730 (6)	0.0587 (5)	0.0630 (5)	−0.0040 (4)	−0.0091 (4)	−0.0066 (4)
O1	0.112 (2)	0.0556 (14)	0.0473 (13)	−0.0128 (13)	−0.0062 (13)	−0.0175 (10)
O2	0.0858 (17)	0.0430 (12)	0.0966 (18)	−0.0307 (12)	0.0023 (14)	−0.0107 (12)
O3	0.0765 (14)	0.0393 (10)	0.0438 (11)	−0.0199 (10)	−0.0116 (10)	0.0006 (8)
N	0.0584 (15)	0.0364 (12)	0.0599 (16)	−0.0107 (11)	−0.0099 (12)	−0.0090 (11)
C1	0.0641 (18)	0.0350 (14)	0.0531 (16)	−0.0199 (13)	−0.0054 (13)	−0.0024 (12)
C2	0.0625 (18)	0.0450 (15)	0.0504 (16)	−0.0239 (13)	0.0007 (13)	−0.0127 (12)
C3	0.0460 (15)	0.0525 (16)	0.0410 (14)	−0.0199 (12)	0.0037 (11)	−0.0078 (12)
C4	0.0489 (15)	0.0438 (14)	0.0412 (14)	−0.0166 (12)	0.0006 (11)	0.0027 (11)
C5	0.0426 (14)	0.0373 (13)	0.0453 (14)	−0.0170 (11)	0.0030 (11)	−0.0065 (11)
C6	0.0453 (14)	0.0415 (14)	0.0376 (13)	−0.0165 (11)	−0.0009 (11)	−0.0020 (11)
C7	0.076 (2)	0.076 (2)	0.0444 (16)	−0.0263 (18)	−0.0025 (15)	−0.0086 (15)
C8	0.0635 (18)	0.0411 (14)	0.0446 (15)	−0.0158 (13)	−0.0059 (13)	0.0023 (12)
C9	0.0617 (18)	0.0477 (16)	0.0449 (15)	−0.0139 (14)	0.0011 (13)	−0.0051 (12)
C10	0.0648 (18)	0.0487 (16)	0.0413 (15)	−0.0218 (14)	−0.0014 (13)	−0.0033 (12)

Geometric parameters (Å, º) top

Cl1—C10	1.721 (3)	C3—C7	1.510 (4)
Cl2—C10	1.717 (3)	C4—C5	1.378 (4)
O1—N	1.216 (3)	C4—H4A	0.9300
O2—N	1.233 (3)	C5—C6	1.398 (4)
O3—C6	1.358 (3)	C7—H7A	0.9600
O3—C8	1.427 (3)	C7—H7B	0.9600
N—C5	1.458 (3)	C7—H7C	0.9600
C1—C2	1.375 (4)	C8—C9	1.484 (4)
C1—C6	1.383 (4)	C8—H8A	0.9700
C1—H1A	0.9300	C8—H8B	0.9700
C2—C3	1.388 (4)	C9—C10	1.307 (4)
C2—H2A	0.9300	C9—H9A	0.9300
C3—C4	1.384 (4)

C6—O3—C8	117.7 (2)	O3—C6—C5	118.1 (2)
O1—N—O2	123.7 (2)	C1—C6—C5	116.9 (2)
O1—N—C5	119.6 (3)	C3—C7—H7A	109.5
O2—N—C5	116.6 (2)	C3—C7—H7B	109.5
C2—C1—C6	120.8 (3)	H7A—C7—H7B	109.5
C2—C1—H1A	119.6	C3—C7—H7C	109.5
C6—C1—H1A	119.6	H7A—C7—H7C	109.5
C1—C2—C3	122.5 (3)	H7B—C7—H7C	109.5
C1—C2—H2A	118.7	O3—C8—C9	105.5 (2)
C3—C2—H2A	118.7	O3—C8—H8A	110.6
C4—C3—C2	116.9 (2)	C9—C8—H8A	110.6
C4—C3—C7	122.2 (3)	O3—C8—H8B	110.6
C2—C3—C7	120.9 (3)	C9—C8—H8B	110.6
C5—C4—C3	120.9 (3)	H8A—C8—H8B	108.8
C5—C4—H4A	119.5	C10—C9—C8	126.3 (3)
C3—C4—H4A	119.5	C10—C9—H9A	116.9
C4—C5—C6	122.0 (3)	C8—C9—H9A	116.9
C4—C5—N	117.7 (2)	C9—C10—Cl2	123.7 (2)
C6—C5—N	120.3 (2)	C9—C10—Cl1	123.2 (2)
O3—C6—C1	124.9 (2)	Cl2—C10—Cl1	113.06 (18)

C6—C1—C2—C3	0.3 (5)	C8—O3—C6—C5	179.3 (2)
C1—C2—C3—C4	−1.3 (4)	C2—C1—C6—O3	178.3 (3)
C1—C2—C3—C7	178.8 (3)	C2—C1—C6—C5	0.7 (4)
C2—C3—C4—C5	1.2 (4)	C4—C5—C6—O3	−178.6 (2)
C7—C3—C4—C5	−178.9 (3)	N—C5—C6—O3	2.5 (4)
C3—C4—C5—C6	−0.2 (4)	C4—C5—C6—C1	−0.8 (4)
C3—C4—C5—N	178.7 (3)	N—C5—C6—C1	−179.7 (3)
O1—N—C5—C4	−140.1 (3)	C6—O3—C8—C9	177.3 (2)
O2—N—C5—C4	38.8 (4)	O3—C8—C9—C10	140.5 (3)
O1—N—C5—C6	38.9 (4)	C8—C9—C10—Cl2	−1.1 (5)
O2—N—C5—C6	−142.3 (3)	C8—C9—C10—Cl1	179.4 (2)
C8—O3—C6—C1	1.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2ⁱ	0.93	2.59	3.241 (4)	127

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₉Cl₂NO₃
M_r	262.08
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5430 (15), 7.7630 (16), 10.713 (2)
α, β, γ (°)	83.69 (3), 88.78 (3), 67.23 (3)
V (Å³)	574.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
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	0.851, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	2277, 2103, 1638
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.156, 1.01
No. of reflections	2103
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.28

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
C1—H1A···O2ⁱ	0.9300	2.5900	3.241 (4)	127.00

Symmetry code: (i) x, y+1, z.

Acknowledgements

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

References

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