1,2 Bis(p nitro­phen­­oxy)ethane

organic papers

o3440

Buttet al. _C

14H12N2O6 doi:10.1107/S1600536806027395 Acta Cryst.(2006). E62, o3440–o3442

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

1,2-Bis(

p

-nitrophenoxy)ethane

M. Saeed Butt,aM. Khawar Rauf,aMichael Bolte,bZareen Akhtera* and M. Zafar-uz-Zamanc

a_{Department of Chemistry, Quaid-i-Azam}

University, Islamabad 45320, Pakistan,b_Institut

fu¨r Anorganische Chemie, J. W. Goethe-Universita¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, andc_National

Engineering and Scientific Commission, PO Box 2801, Islamabad, Pakistan

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 173 K

Mean(C–C) = 0.002 A˚

Rfactor = 0.036

wRfactor = 0.102

Data-to-parameter ratio = 14.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 19 June 2006 Accepted 14 July 2006

#2006 International Union of Crystallography All rights reserved

Molecules of the title compound, C14H12N2O6, are located on

centres of inversion. The molecule is essentially planar, with the exception of the nitro group, which is twisted slightly out of the plane of the remaining atoms.

Comment

Polyimides form a very interesting group of mechanically, chemically and heat-resistant polymers (Lee & Jung, 1998). In many cases, polyimides are insoluble and do not react below their decomposition temperatures. On the other hand, their resistivity complicates their processing for technical applica-tions. For these reasons their application as engineering materials is restricted (Im & Jung, 2000). Therefore, efforts have been made to improve their processability while main-taining their excellent thermal and mechanical properties (Cholet al., 2001).

For example, bulky lateral substituents (Yang et al., 2000), flexible alkyl side chains (Jung & Park, 1996), non-coplanar biphenyl groups, and flexible alkyl or aryl ether spacers (Liaw

et al., 1998) have been used to enhance solubility and thus processability. Incorporation of flexible segments such as –O–, –SO2–, –CH2– and –C(CF3)2–, and of bulky pendant groups

such astert-butyl and adamantyl, were found to be successful in altering crystallinity and intermolecular interactions to increase solubility (Eastmond et al., 1996). Bulky pendant groups increase the disorder in chains and hinder dense chain packing. This is concomitant with reduction of crystallinity and enhancement of solubility. Unfortunately, while the solubility of non-coplanar structures with pendant aliphatic segments is enhanced, the thermal properties of such substances are usually worsened.

Recently, Hsio et al. (1997) reported some soluble ther-moplastic polyimides derived from spiro-linked diamine structures in an effort to overcome this problem. The latter polymers had glass transition temperatures between 509 and 529 K and withstood temperatures up to 723 K (in N2). The

enhanced solubility of the polymer is expected to result (Hedrich, 1992).

The molecules of the title compound, (I), are located on centres of inversion. Geometric parameters are normal. All the non-H atoms apart from the nitro groups lie in a common plane with an r.m.s. deviation of 0.0128 A˚ (Khawar Raufet al., 2006). The NO2group makes a dihedral angle of 12.15 (13)

with the mean plane through the benzene ring (see also Table 1). The crystal structure is stabilized by a C—H O hydrogen bond (Table 2).

Experimental

p-Nitrophenol (8.0 g, 0.057 mol) and anhydrous potassium carbonate (7.86 g, 0.057 mol) were suspended in a mixture of N,N0

-dimethyl-formamide (50 ml) and toluene (30 ml). The mixture was refluxed at 473 K with a Dean–Stark trap for azeotropic removal of water. When most of the toluene had been removed, 1,2-dichloroethane (2.35 ml, 0.0285 mol) was added to the mixture, which was then refluxed for 12 h. The resulting solution was allowed to cool to room temperature and then it was poured into 300 ml of methanol–water (1:1) to give a yellow precipitate. After repeated washing with water, the product was separated by filtration and recrystallized from ethanol in 83% yield (m.p. 432 K).

Crystal data

C14H12N2O6

Mr= 304.26

Monoclinic,P21=n

a= 9.1465 (12) A˚ b= 7.3137 (7) A˚ c= 10.2852 (13) A˚

= 93.353 (10) V= 686.85 (14) A˚3

Z= 2

Dx= 1.471 Mg m

3

MoKradiation

= 0.12 mm1

T= 173 (2) K Block, light yellow 0.490.460.44 mm

Data collection

Stoe IPDS II two-circle diffractometer

!scans

Absorption correction: none 8567 measured reflections

1477 independent reflections 1380 reflections withI> 2(I) Rint= 0.037

max= 27.0

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.036}

wR(F2_{) = 0.103}

S= 1.08 1477 reflections 101 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0586P)2

+ 0.1845P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.37 e A˚

3

min=0.20 e A˚

3

Extinction correction:SHELXL97 Extinction coefficient: 0.11 (2)

Table 1

Selected torsion angles (_).

O3—N1—C4—C3 168.86 (10) O2—N1—C4—C3 11.59 (15)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C3—H3 O3i

0.95 2.48 3.4166 (14) 169

Symmetry code: (i)xþ1 2;yþ

1 2;zþ

3 2.

All the H atoms were located in a difference map. However, they were refined using a riding model, with C—H = 0.95 and 0.99 A˚ for aryl and methylene H atoms, respectively.Uiso(H) values were set to

1.2Ueq(C).

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:XPin

organic papers

Acta Cryst.(2006). E62, o3440–o3442 Buttet al. _C

[image:2.610.44.294.68.260.2]

14H12N2O6

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Figure 1

Molecular structure of (I). Displacement ellipsoids are drawn at the 50%

[image:2.610.47.294.300.571.2]

probability level. [Symmetry code: (A)x+ 2,y+ 1,z+ 1.]

Figure 2

SHELXTL-Plus(Sheldrick, 1991); software used to prepare material for publication:SHELXL97.

The authors are grateful to the Department of Chemistry, Quaid-I-Azam University, Islamabad, and to the National Engineering and Scientific Commission, Islamabad, Pakistan, for providing laboratory and analytical facilities.

References

Chol, K. H., Lee, K. H. & Jung, J. C. (2001).J. Polym. Sci. Part A: Polym. Chem.39, 3818–3825.

Eastmond, G., Paprotny, C. & Irwin, R. S. (1996).Macromolecules,29, 1382– 1388.

Hedrich, J. L. (1992).Polymer,33, 1399–1405.

Hsio, S. H., Yang, C. P. & Yang, C. Y. (1997).J. Polym. Sci. Part A Polym. Chem.35, 1487–1497.

Im, J. K. & Jung, J. C. (2000).Polymer,41, 8709–8716.

Jung, J. C. & Park, S. B. (1996).J. Polym. Sci. Part A Polym. Chem.34, 357–365. Khawar Rauf, M., Badshah, A. & Bolte, M. (2006).Acta Cryst.E62, o1859–

o1860.

Lee, K. H. & Jung, J. C. (1998).Polym. Bull.40, 407–414.

Liaw, D. J., Liaw, B. Y. & Jeng, M. Q. (1998).Polymer,39, 1597–1607. Sheldrick, G. M. (1991).SHELXTL-Plus. Release 4.1. Siemens Analytical

X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Stoe & Cie (2001).X-AREA. Stoe & Cie, Darmstadt, Germany.

Yang, C. P., Hsiao, S. H. & Yang, H. W. (2000).Macromol. Chem. Phys.201, 409–418.

organic papers

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Buttet al. _C

supporting information

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Acta Cryst. (2006). E62, o3440–o3442

supporting information

Acta Cryst. (2006). E62, o3440–o3442 [https://doi.org/10.1107/S1600536806027395]

1,2-Bis(

p

-nitrophenoxy)ethane

M. Saeed Butt, M. Khawar Rauf, Michael Bolte, Zareen Akhter and M. Zafar-uz-Zaman

1,2-Bis(p-nitrophenoxy)ethylene

Crystal data

C14H12N2O6

Mr = 304.26 Monoclinic, P21/n

Hall symbol: -P 2yn a = 9.1465 (12) Å b = 7.3137 (7) Å c = 10.2852 (13) Å β = 93.353 (10)° V = 686.85 (14) Å3

Z = 2

F(000) = 316 Dx = 1.471 Mg m−3

Melting point: 432 K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 8996 reflections θ = 3.6–27.2°

µ = 0.12 mm−1

T = 173 K

Block, light yellow 0.49 × 0.46 × 0.44 mm

Data collection

Stoe IPDS-II two-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

8567 measured reflections 1477 independent reflections

1380 reflections with I > 2σ(I) Rint = 0.037

θmax = 27.0°, θmin = 4.0°

h = −11→11 k = −9→8 l = −13→13

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.036}

wR(F2_{) = 0.103}

S = 1.08 1477 reflections 101 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_(F

o2) + (0.0586P)2 + 0.1845P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.37 e Å−3

Δρmin = −0.20 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.11 (2)

Special details

supporting information

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Acta Cryst. (2006). E62, o3440–o3442

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

N1 0.32402 (10) 0.57146 (14) 0.80918 (9) 0.0217 (3) O1 0.82156 (8) 0.59629 (11) 0.51718 (7) 0.0210 (2) O2 0.21184 (9) 0.64765 (14) 0.76280 (9) 0.0322 (3) O3 0.32999 (9) 0.48898 (12) 0.91408 (8) 0.0286 (3) C1 0.70374 (11) 0.58452 (14) 0.59315 (10) 0.0174 (3) C2 0.58574 (11) 0.70123 (14) 0.55763 (10) 0.0190 (3)

H2 0.5916 0.7824 0.4860 0.023*

C3 0.46058 (11) 0.69710 (15) 0.62798 (10) 0.0197 (3)

H3 0.3792 0.7732 0.6041 0.024*

C4 0.45655 (11) 0.57869 (15) 0.73473 (10) 0.0192 (3) C5 0.57319 (12) 0.46538 (16) 0.77235 (11) 0.0227 (3)

H5 0.5683 0.3879 0.8461 0.027*

C6 0.69805 (11) 0.46696 (16) 0.70017 (11) 0.0223 (3)

H6 0.7784 0.3889 0.7235 0.027*

C7 0.94301 (11) 0.47511 (15) 0.54757 (11) 0.0211 (3)

H7A 0.9125 0.3459 0.5363 0.025*

H7B 0.9821 0.4933 0.6385 0.025*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

N1 0.0185 (5) 0.0250 (5) 0.0222 (5) −0.0030 (3) 0.0047 (3) −0.0054 (4) O1 0.0141 (4) 0.0242 (4) 0.0255 (4) 0.0051 (3) 0.0061 (3) 0.0052 (3) O2 0.0172 (4) 0.0468 (6) 0.0330 (5) 0.0046 (4) 0.0054 (3) −0.0015 (4) O3 0.0288 (5) 0.0335 (5) 0.0243 (4) −0.0050 (3) 0.0093 (3) 0.0001 (3) C1 0.0135 (5) 0.0191 (5) 0.0197 (5) −0.0008 (4) 0.0022 (4) −0.0024 (4) C2 0.0178 (5) 0.0194 (5) 0.0198 (5) 0.0015 (4) 0.0017 (4) 0.0011 (4) C3 0.0152 (5) 0.0214 (5) 0.0224 (5) 0.0030 (4) 0.0005 (4) −0.0022 (4) C4 0.0153 (5) 0.0230 (5) 0.0198 (5) −0.0028 (4) 0.0043 (4) −0.0043 (4) C5 0.0216 (5) 0.0258 (6) 0.0211 (5) 0.0000 (4) 0.0034 (4) 0.0037 (4) C6 0.0174 (5) 0.0248 (6) 0.0246 (6) 0.0043 (4) 0.0018 (4) 0.0043 (4) C7 0.0142 (5) 0.0226 (5) 0.0269 (6) 0.0042 (4) 0.0044 (4) 0.0036 (4)

Geometric parameters (Å, º)

N1—O3 1.2346 (13) C3—C4 1.4006 (15)

N1—O2 1.2384 (13) C3—H3 0.9500

N1—C4 1.4721 (13) C4—C5 1.3879 (16)

O1—C1 1.3703 (12) C5—C6 1.3981 (14)

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Acta Cryst. (2006). E62, o3440–o3442

C1—C6 1.4000 (15) C6—H6 0.9500

C1—C2 1.4074 (14) C7—C7i _{1.515 (2)}

C2—C3 1.3899 (14) C7—H7A 0.9900

C2—H2 0.9500 C7—H7B 0.9900

O3—N1—O2 123.35 (9) C5—C4—N1 118.46 (10)

O3—N1—C4 118.45 (9) C3—C4—N1 119.36 (9)

O2—N1—C4 118.19 (9) C4—C5—C6 119.05 (10)

C1—O1—C7 117.36 (8) C4—C5—H5 120.5

O1—C1—C6 123.61 (9) C6—C5—H5 120.5

O1—C1—C2 115.50 (9) C5—C6—C1 119.44 (10)

C6—C1—C2 120.89 (9) C5—C6—H6 120.3

C3—C2—C1 119.61 (10) C1—C6—H6 120.3

C3—C2—H2 120.2 O1—C7—C7i _{105.24 (11)}

C1—C2—H2 120.2 O1—C7—H7A 110.7

C2—C3—C4 118.80 (9) C7i_{—C7—H7A 110.7}

C2—C3—H3 120.6 O1—C7—H7B 110.7

C4—C3—H3 120.6 C7i_{—C7—H7B 110.7}

C5—C4—C3 122.19 (10) H7A—C7—H7B 108.8

C7—O1—C1—C6 2.41 (15) O3—N1—C4—C3 −168.86 (10) C7—O1—C1—C2 −178.10 (9) O2—N1—C4—C3 11.59 (15) O1—C1—C2—C3 179.13 (9) C3—C4—C5—C6 −1.09 (17) C6—C1—C2—C3 −1.36 (16) N1—C4—C5—C6 178.14 (9) C1—C2—C3—C4 1.31 (15) C4—C5—C6—C1 1.03 (17) C2—C3—C4—C5 −0.10 (16) O1—C1—C6—C5 179.64 (10) C2—C3—C4—N1 −179.31 (9) C2—C1—C6—C5 0.17 (17) O3—N1—C4—C5 11.90 (15) C1—O1—C7—C7i _{−177.67 (10)}

O2—N1—C4—C5 −167.66 (10)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C3—H3···O3ii _{0.95 2.48 3.4166 (14) 169}