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

Abstract

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,

• a = 4.0210 (8) Å

• b = 21.506 (4) Å

• c = 12.333 (3) Å

• β = 96.41 (3)°

• V = 1059.8 (4) ų

• 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[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812010070/vm2161Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

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 U_iso(H) = xU_eq(C), where x = 1.2 for aromatic H and x = 1.5 for other H.

Figures

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.

Crystal data

C9H7Cl2NO3	F(000) = 504
Mr = 248.06	Dx = 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

Enraf–Nonius CAD-4 diffractometer	1416 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 25.4°, θmin = 1.9°
ω/2θ scans	h = 0→4
Absorption correction: ψ scan (North et al., 1968)	k = −25→25
Tmin = 0.841, Tmax = 0.943	l = −14→14
4390 measured reflections	3 standard reflections every 200 reflections
1941 independent reflections	intensity decay: 1%

Refinement

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(Fo2) + (0.1P)2 + 0.2P] where P = (Fo2 + 2Fc2)/3
1941 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.29 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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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