1-(2-Methoxy­ethoxy)-4-nitro­benzene

Liu, Y.; Xu, W.-N.; Zhang, X.-L.; Ma, J.-P.; Guo, D.-S.

doi:10.1107/S1600536807061636

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o12

https://doi.org/10.1107/S1600536807061636

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1-(2-Methoxyethoxy)-4-nitrobenzene

Yang Liu,^a Wei-Na Xu,^a Xiao-Ling Zhang,^a Jian-Ping Ma ^a and Dian-Shun Guo ^a ^*

^aDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: chdsguo@sdnu.edu.cn

(Received 20 November 2007; accepted 21 November 2007; online 6 December 2007)

The title compound, C₉H₁₁NO₄, is an intermediate for dyes and drugs. The O—C—C—O chain adopts a synclinal conformation. The crystal structure is stabilized by C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Guo et al. (2006 ); Higson (1992 ).

Experimental

Crystal data

C₉H₁₁NO₄
M_r = 197.19
Orthorhombic, P n a 2₁
a = 11.280 (3) Å
b = 20.430 (5) Å
c = 4.1079 (10) Å
V = 946.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 (2) K
0.49 × 0.43 × 0.38 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.948, T_max = 0.959
4034 measured reflections
1023 independent reflections
982 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 1.05
1023 reflections
130 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.12 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: 2 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.93	2.65	3.419 (3)	140
C3—H3⋯O3ⁱⁱ	0.93	2.50	3.317 (2)	147
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+1]$ ; (ii) $[-x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807061636/bt2633sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807061636/bt2633Isup2.hkl

checkCIF report

Comment top

Nitroaromatic compounds are widely used as pesticides, explosives, and precursors for dyes and many pharmaceutical agents (Higson, 1992). Recently, we described the structure of a nitrobenzene derivative containing a polyether linkage which can be used as an asymmetric alkylating agent (Guo et al., 2006). Herein, we report the structure of another nitrobenzene derivative, in which an asymmetric ethylene glycol ether strand is appended to the para position of nitro group.

The title compound consists of an ethylene glycol monomethyl ether unit and a nitro-substituted benzene ring (Fig. 1). In the crystal structure the nitro group is coplanar with the benzene ring. Interestingly, there are two intermolecular hydrogen bonds (Table 1).

Related literature top

For related literature, see: Guo et al. (2006); Higson (1992).

Experimental top

To a mixture of 2-methoxyethanol (0.190 ml, 2.40 mmol) and potassium hydroxide (0.120 g, 3.00 mmol) in DMSO (5 ml), was added a solution of 1-chloro-4-nitrobenzene (0.315 g, 2.00 mmol) in DMSO (5 ml). The resulting mixture was stirred for 20 h at 333 K and cooled to room temperature. The reaction mixture was poured into HCl 5% solution. The precipitate was filtered off and washed with water. After drying in vacuum, the title compound was obtained as a yellow solid in 90% yield. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of anhydrous ethanol at 273 K.

Structure description top

For related literature, see: Guo et al. (2006); Higson (1992).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

1-(2-Methoxyethoxy)-4-nitrobenzene top

Crystal data top

C₉H₁₁NO₄	D_x = 1.384 Mg m⁻³
M_r = 197.19	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 2528 reflections
a = 11.280 (3) Å	θ = 2.7–27.8°
b = 20.430 (5) Å	µ = 0.11 mm⁻¹
c = 4.1079 (10) Å	T = 100 K
V = 946.7 (4) Å³	Block, colourless
Z = 4	0.49 × 0.43 × 0.38 mm
F(000) = 416

Data collection top

Bruker SMART CCD area-detector diffractometer	1023 independent reflections
Radiation source: fine-focus sealed tube	982 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
phi and ω scans	θ_max = 25.7°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −12→13
T_min = 0.948, T_max = 0.959	k = −15→24
4034 measured reflections	l = −4→4

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0395P)² + 0.1764P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.13 e Å⁻³
1023 reflections	Δρ_min = −0.12 e Å⁻³
130 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.032 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 2 (1)

Crystal data top

C₉H₁₁NO₄	V = 946.7 (4) Å³
M_r = 197.19	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 11.280 (3) Å	µ = 0.11 mm⁻¹
b = 20.430 (5) Å	T = 100 K
c = 4.1079 (10) Å	0.49 × 0.43 × 0.38 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1023 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	982 reflections with I > 2σ(I)
T_min = 0.948, T_max = 0.959	R_int = 0.030
4034 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.079	Δρ_max = 0.13 e Å⁻³
S = 1.05	Δρ_min = −0.12 e Å⁻³
1023 reflections	Absolute structure: Flack (1983)
130 parameters	Absolute structure parameter: 2 (1)
1 restraint

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
C1	−0.05088 (16)	0.68859 (9)	−0.1216 (7)	0.0407 (5)
C2	−0.08278 (16)	0.62314 (9)	−0.1160 (6)	0.0373 (5)
H2	−0.1522	0.6090	−0.2160	0.045*
C3	−0.00976 (16)	0.57971 (9)	0.0401 (6)	0.0341 (5)
H3	−0.0303	0.5357	0.0490	0.041*
C4	0.09501 (15)	0.60085 (8)	0.1858 (6)	0.0310 (5)
C5	0.12605 (16)	0.66669 (9)	0.1780 (6)	0.0382 (5)
H5	0.1956	0.6811	0.2762	0.046*
C6	0.05189 (18)	0.71044 (9)	0.0221 (7)	0.0446 (6)
H6	0.0715	0.7546	0.0143	0.054*
C7	0.27095 (16)	0.57084 (10)	0.4767 (6)	0.0363 (5)
H7A	0.2588	0.6054	0.6354	0.044*
H7B	0.3259	0.5866	0.3127	0.044*
C8	0.31983 (17)	0.51107 (10)	0.6395 (6)	0.0411 (5)
H8A	0.3888	0.5228	0.7677	0.049*
H8B	0.2608	0.4928	0.7851	0.049*
C9	0.3945 (2)	0.40593 (11)	0.5514 (9)	0.0536 (7)
H9A	0.4592	0.4164	0.6939	0.080*
H9B	0.4212	0.3762	0.3858	0.080*
H9C	0.3319	0.3858	0.6744	0.080*
N1	−0.12710 (18)	0.73499 (9)	−0.2931 (7)	0.0580 (6)
O1	−0.21750 (15)	0.71456 (9)	−0.4228 (6)	0.0687 (6)
O2	−0.09783 (16)	0.79250 (8)	−0.3004 (9)	0.0948 (10)
O3	0.16033 (10)	0.55315 (6)	0.3289 (4)	0.0354 (4)
O4	0.35171 (11)	0.46405 (7)	0.4039 (4)	0.0414 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0379 (10)	0.0363 (10)	0.0479 (14)	0.0084 (8)	0.0100 (11)	0.0041 (11)
C2	0.0314 (8)	0.0389 (10)	0.0418 (12)	0.0007 (7)	0.0028 (10)	−0.0049 (11)
C3	0.0333 (9)	0.0295 (8)	0.0396 (11)	−0.0048 (7)	0.0042 (9)	−0.0033 (10)
C4	0.0296 (9)	0.0298 (9)	0.0336 (11)	−0.0002 (7)	0.0077 (8)	−0.0041 (9)
C5	0.0335 (9)	0.0320 (9)	0.0490 (14)	−0.0071 (7)	0.0042 (10)	−0.0042 (11)
C6	0.0444 (11)	0.0268 (9)	0.0626 (16)	−0.0005 (8)	0.0092 (12)	0.0013 (11)
C7	0.0317 (9)	0.0415 (10)	0.0357 (13)	−0.0061 (8)	0.0023 (9)	−0.0074 (9)
C8	0.0382 (10)	0.0512 (12)	0.0338 (12)	−0.0022 (9)	−0.0032 (10)	−0.0010 (11)
C9	0.0465 (11)	0.0506 (12)	0.0637 (17)	0.0076 (9)	−0.0042 (13)	0.0163 (14)
N1	0.0531 (11)	0.0456 (11)	0.0752 (18)	0.0149 (9)	0.0053 (12)	0.0099 (13)
O1	0.0553 (10)	0.0677 (11)	0.0830 (15)	0.0171 (8)	−0.0121 (12)	0.0117 (13)
O2	0.0856 (13)	0.0423 (9)	0.157 (3)	0.0116 (8)	−0.0187 (18)	0.0259 (15)
O3	0.0298 (6)	0.0289 (6)	0.0474 (10)	−0.0041 (5)	−0.0013 (7)	0.0000 (7)
O4	0.0450 (7)	0.0415 (7)	0.0376 (8)	0.0067 (6)	−0.0007 (8)	0.0043 (7)

Geometric parameters (Å, º) top

C1—C6	1.375 (3)	C7—C8	1.497 (3)
C1—C2	1.385 (3)	C7—H7A	0.9700
C1—N1	1.461 (3)	C7—H7B	0.9700
C2—C3	1.370 (3)	C8—O4	1.410 (3)
C2—H2	0.9300	C8—H8A	0.9700
C3—C4	1.393 (3)	C8—H8B	0.9700
C3—H3	0.9300	C9—O4	1.418 (3)
C4—O3	1.356 (2)	C9—H9A	0.9600
C4—C5	1.390 (2)	C9—H9B	0.9600
C5—C6	1.382 (3)	C9—H9C	0.9600
C5—H5	0.9300	N1—O2	1.221 (2)
C6—H6	0.9300	N1—O1	1.224 (3)
C7—O3	1.434 (2)

C6—C1—C2	121.69 (19)	O3—C7—H7B	110.2
C6—C1—N1	119.50 (18)	C8—C7—H7B	110.2
C2—C1—N1	118.8 (2)	H7A—C7—H7B	108.5
C3—C2—C1	118.48 (19)	O4—C8—C7	110.1 (2)
C3—C2—H2	120.8	O4—C8—H8A	109.6
C1—C2—H2	120.8	C7—C8—H8A	109.6
C2—C3—C4	120.68 (17)	O4—C8—H8B	109.6
C2—C3—H3	119.7	C7—C8—H8B	109.6
C4—C3—H3	119.7	H8A—C8—H8B	108.2
O3—C4—C5	124.65 (18)	O4—C9—H9A	109.5
O3—C4—C3	115.11 (15)	O4—C9—H9B	109.5
C5—C4—C3	120.25 (19)	H9A—C9—H9B	109.5
C6—C5—C4	118.95 (19)	O4—C9—H9C	109.5
C6—C5—H5	120.5	H9A—C9—H9C	109.5
C4—C5—H5	120.5	H9B—C9—H9C	109.5
C1—C6—C5	119.96 (18)	O2—N1—O1	122.9 (2)
C1—C6—H6	120.0	O2—N1—C1	118.5 (2)
C5—C6—H6	120.0	O1—N1—C1	118.61 (18)
O3—C7—C8	107.69 (15)	C4—O3—C7	118.38 (14)
O3—C7—H7A	110.2	C8—O4—C9	111.3 (2)
C8—C7—H7A	110.2

C6—C1—C2—C3	0.6 (4)	O3—C7—C8—O4	67.3 (2)
N1—C1—C2—C3	178.8 (2)	C6—C1—N1—O2	−0.9 (4)
C1—C2—C3—C4	−0.9 (3)	C2—C1—N1—O2	−179.2 (3)
C2—C3—C4—O3	−179.2 (2)	C6—C1—N1—O1	179.2 (3)
C2—C3—C4—C5	0.8 (3)	C2—C1—N1—O1	0.9 (4)
O3—C4—C5—C6	179.6 (2)	C5—C4—O3—C7	−1.6 (3)
C3—C4—C5—C6	−0.4 (3)	C3—C4—O3—C7	178.42 (19)
C2—C1—C6—C5	−0.2 (4)	C8—C7—O3—C4	175.33 (18)
N1—C1—C6—C5	−178.4 (2)	C7—C8—O4—C9	−177.94 (16)
C4—C5—C6—C1	0.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.93	2.65	3.419 (3)	140
C3—H3···O3ⁱⁱ	0.93	2.50	3.317 (2)	147

Symmetry codes: (i) x+1/2, −y+3/2, z+1; (ii) −x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₄
M_r	197.19
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	11.280 (3), 20.430 (5), 4.1079 (10)
V (Å³)	946.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.49 × 0.43 × 0.38

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.948, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	4034, 1023, 982
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.05
No. of reflections	1023
No. of parameters	130
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.12
Absolute structure	Flack (1983)
Absolute structure parameter	2 (1)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.93	2.65	3.419 (3)	140.1
C3—H3···O3ⁱⁱ	0.93	2.50	3.317 (2)	146.5

Symmetry codes: (i) x+1/2, −y+3/2, z+1; (ii) −x, −y+1, z−1/2.

Acknowledgements

Financial support by the National Natural Science Foundation of China (No. 20572064) and Shandong Province Natural Science Foundation (Y2006B30) is gratefully acknowledged.

References

Bruker (1999). SMART (Version 5.6), SAINT (Version 5.A06) and SADABS (Version 2.01). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Guo, D.-S., Zhang, X.-Y., Liu, Z.-P. & Ma, J.-P. (2006). Acta Cryst. E62, o3655–o3656. Web of Science CSD CrossRef IUCr Journals Google Scholar
Higson, F. K. (1992). Adv. Appl. Microbiol. 37, 1–19. CrossRef PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar