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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1122.
Published online 2008 May 21. doi:  10.1107/S1600536808014736
PMCID: PMC2961458

1,2-Bis(4-amino­phen­oxy)ethane

Abstract

The mol­ecule of the title compound, C14H16N2O2, is located on a crystallographic twofold rotation axis. The central O—C—C—O bridge adopts a gauche conformation. One of the amine H atoms is disordered over two equally occupied positions. The crystal structure is stabilized by N—H(...)O and N—H(...)N hydrogen bonds.

Related literature

For related literature, see: Barikani & Mehdipour-Ataei (2000 [triangle]); Eastmond & Paprotny (1999 [triangle]); Hsio et al. (1997 [triangle]); Liaw & Liaw (2001 [triangle]); Yang & Chen (1993 [triangle]); Hergenrother et al. (2002 [triangle]).

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Object name is e-64-o1122-scheme1.jpg

Experimental

Crystal data

  • C14H16N2O2
  • M r = 244.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1122-efi2.jpg
  • a = 14.2157 (9) Å
  • b = 10.4608 (8) Å
  • c = 8.1817 (5) Å
  • V = 1216.68 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 173 (2) K
  • 0.37 × 0.35 × 0.23 mm

Data collection

  • Stoe IPDSII two-circle diffractometer
  • Absorption correction: none
  • 15103 measured reflections
  • 1700 independent reflections
  • 1549 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.119
  • S = 1.20
  • 1700 reflections
  • 95 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014736/zl2110sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014736/zl2110Isup2.hkl

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

Acknowledgments

The authors are grateful to the Department of Chemistry, Quaid-I-Azam University, Islamabad, Pakistan, and to the Institute for Inorganic Chemistry, University of Frankfurt, Germany, for providing laboratory and analytical facilities.

supplementary crystallographic information

Comment

Aromatic polyimides are well accepted as high performance and heat resistant materials (Hergenrother et al., 2000). They exhibit a favorable balance of physical and chemical properties, show excellent thermal, mechanical and electrical properties and are thus widely used in microelectronics and aerospace engineering (Eastmond & Paprotny, 1999). However, the technological and industrial application of rigid polyimides are limited by processing difficulties due to their high melting or glass transition temperatures and their lack of solubility in most organic solvents (Hsio et al., 1997). Strong interactions between polyimide chains and their rigid structures are the main reason for these behaviors. To overcome such a drawback, different methods have been introduced to modifiy their structures. Many efforts have been made in designing and synthesizing new dianhydrides (Eastmond & Paprotny, 1999) and diamines (Yang & Chen, 1993), and therefore producing a great variety of more soluble and processable polyimides for various purposes and applications. Incorporation of flexible units such as –NHCO–, –O–, (Barikani & Mehdipour-Ataei, 2000), –CO– and –SO2- is one of the most important approaches to overcome these processing problems (Liaw & Liaw, 2001). The title compound is such a new starting material for the synthesis of high performance polyimides.

Molecules of the title compound, C14H16N2O4, are located on a crystallographic twofold rotation axis. The central O—C—C—O bridge adopts a gauche conformation. One of the amino H atoms is disordered over two equally occupied positions. As a result of that, neighbouring molecules are connected by alternating hydrogen bonds, either N1-H1B···N1ii or N1-H1C···N1iii, because H1B and H1C and their symmetry equivalents would be too close to each other and would be mutually exclusive (symmetry codes: see Table 1). In addition, the crystal structure is stabilized by N—H···O hydrogen bonds (Table 1).

Experimental

A two neck 250 ml round bottom flask was charged with 1 g of 1,2-di(p-nitrophenyloxy) ethylene (3.28 mmoles), 10 ml of hydrazine monohydrate, 80 ml of ethanol and 0.06 g of 5% palladium on carbon (Pd/C).The mixture was heated to reflux for 16 h and then filtered to remove Pd/C and the crude solid was recrystallized from ethanol to yield 92.2% of the diamine, m.p. 352K.

Refinement

All H atoms could be located by difference Fourier synthesis but were ultimately placed in calculated positions using a riding model with C—H(aromatic) = 0.95 Å or CH(methylene) = 0.99 Å with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C). The amino H atoms were freely refined. One of the amino H atoms is disordered over two equally occupied positions.

Figures

Fig. 1.
The structure of the title compound showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and only one of the two alternative types of N-H hydrogen atoms is shown. Symmetry code for generating equivalent atoms: ...

Crystal data

C14H16N2O2Dx = 1.334 Mg m3
Mr = 244.29Melting point: 179 K
Orthorhombic, PbcnMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 14232 reflections
a = 14.2157 (9) Åθ = 3.5–29.7º
b = 10.4608 (8) ŵ = 0.09 mm1
c = 8.1817 (5) ÅT = 173 (2) K
V = 1216.68 (14) Å3Block, dark red
Z = 40.37 × 0.35 × 0.23 mm
F000 = 520

Data collection

Stoe IPDSII two-circle diffractometer1549 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.049
Monochromator: graphiteθmax = 29.6º
T = 173(2) Kθmin = 3.5º
ω scansh = −19→19
Absorption correction: nonek = −14→11
15103 measured reflectionsl = −11→11
1700 independent reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.048  w = 1/[σ2(Fo2) + (0.0299P)2 + 0.7945P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.119(Δ/σ)max < 0.001
S = 1.20Δρmax = 0.29 e Å3
1700 reflectionsΔρmin = −0.19 e Å3
95 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (2)
Secondary atom site location: difference Fourier map

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 (Å2)

xyzUiso*/UeqOcc. (<1)
O10.91391 (6)0.60429 (10)0.65677 (12)0.0243 (3)
N10.52550 (9)0.65323 (15)0.5428 (2)0.0332 (3)
H1A0.5093 (15)0.718 (2)0.470 (3)0.048 (6)*
H1B0.496 (3)0.573 (4)0.537 (5)0.042 (11)*0.50
H1C0.486 (3)0.650 (4)0.638 (6)0.048 (12)*0.50
C10.81695 (9)0.61092 (12)0.63296 (15)0.0198 (3)
C20.78489 (9)0.71034 (13)0.53437 (17)0.0232 (3)
H20.82850.76840.48720.028*
C30.68899 (10)0.72479 (13)0.50483 (17)0.0239 (3)
H30.66780.79310.43770.029*
C40.62345 (9)0.64020 (13)0.57255 (17)0.0234 (3)
C50.65662 (10)0.54140 (14)0.67195 (19)0.0268 (3)
H50.61310.48350.71960.032*
C60.75275 (10)0.52624 (13)0.70255 (17)0.0240 (3)
H60.77420.45860.77040.029*
C70.94691 (9)0.49765 (13)0.75075 (18)0.0244 (3)
H7A0.92300.41690.70330.029*
H7B0.92370.50430.86450.029*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0192 (4)0.0272 (5)0.0264 (5)−0.0010 (4)−0.0026 (4)0.0063 (4)
N10.0205 (6)0.0377 (7)0.0413 (8)0.0012 (5)−0.0023 (5)0.0043 (6)
C10.0202 (6)0.0214 (6)0.0178 (5)−0.0003 (5)−0.0017 (4)−0.0017 (5)
C20.0231 (6)0.0230 (6)0.0235 (6)−0.0010 (5)0.0019 (5)0.0039 (5)
C30.0246 (6)0.0239 (6)0.0233 (6)0.0036 (5)−0.0001 (5)0.0028 (5)
C40.0205 (6)0.0254 (6)0.0244 (6)0.0005 (5)−0.0010 (5)−0.0028 (5)
C50.0228 (6)0.0267 (6)0.0310 (7)−0.0048 (5)−0.0004 (5)0.0043 (6)
C60.0247 (6)0.0223 (6)0.0250 (6)−0.0023 (5)−0.0033 (5)0.0050 (5)
C70.0237 (6)0.0233 (6)0.0261 (6)−0.0007 (5)−0.0050 (5)0.0024 (5)

Geometric parameters (Å, °)

O1—C11.3938 (15)C3—C41.3992 (19)
O1—C71.4338 (16)C3—H30.9500
N1—C41.4202 (18)C4—C51.397 (2)
N1—H1A0.93 (2)C5—C61.3983 (19)
N1—H1B0.94 (4)C5—H50.9500
N1—H1C0.96 (5)C6—H60.9500
C1—C21.3928 (18)C7—C7i1.510 (2)
C1—C61.3935 (18)C7—H7A0.9900
C2—C31.3927 (18)C7—H7B0.9900
C2—H20.9500
C1—O1—C7115.93 (10)C5—C4—C3118.27 (12)
C4—N1—H1A115.0 (14)C5—C4—N1120.12 (13)
C4—N1—H1B112 (3)C3—C4—N1121.61 (13)
H1A—N1—H1B120 (3)C4—C5—C6121.20 (12)
C4—N1—H1C115 (3)C4—C5—H5119.4
H1A—N1—H1C114 (3)C6—C5—H5119.4
H1B—N1—H1C75 (3)C1—C6—C5119.65 (12)
C2—C1—C6119.80 (12)C1—C6—H6120.2
C2—C1—O1116.21 (11)C5—C6—H6120.2
C6—C1—O1123.98 (12)O1—C7—C7i108.83 (10)
C3—C2—C1120.12 (12)O1—C7—H7A109.9
C3—C2—H2119.9C7i—C7—H7A109.9
C1—C2—H2119.9O1—C7—H7B109.9
C2—C3—C4120.96 (12)C7i—C7—H7B109.9
C2—C3—H3119.5H7A—C7—H7B108.3
C4—C3—H3119.5
C7—O1—C1—C2−176.63 (12)C3—C4—C5—C6−0.5 (2)
C7—O1—C1—C64.11 (19)N1—C4—C5—C6179.72 (14)
C6—C1—C2—C3−0.3 (2)C2—C1—C6—C50.4 (2)
O1—C1—C2—C3−179.57 (12)O1—C1—C6—C5179.62 (13)
C1—C2—C3—C4−0.2 (2)C4—C5—C6—C10.0 (2)
C2—C3—C4—C50.6 (2)C1—O1—C7—C7i174.05 (12)
C2—C3—C4—N1−179.62 (14)

Symmetry codes: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1ii0.93 (2)2.53 (2)3.4082 (18)158.6 (18)
N1—H1B···N1iii0.94 (4)2.48 (4)3.360 (3)157 (4)
N1—H1C···N1iv0.96 (5)2.61 (5)3.468 (3)148 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2110).

References

  • Barikani, M. & Mehdipour-Ataei, S. (2000). J. Polym. Sci. A Polym. Chem.38, 1487–1492.
  • Eastmond, G. C. & Paprotny, J. (1999). Eur. Polym. J.35, 2097–2106.
  • Hergenrother, P. M., Watson, K. A., Smith, J. G., Connell, J. W. & Yokota, R. (20021). Polymer, 41, 5073–5081.
  • Hsio, S. H., Yang, C. P. & Chu, K. Y. (1997). Macromolecules, 30, 165–170.
  • Liaw, D. J. & Liaw, B. Y. (2001). Polymer, 2, 839–845.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.
  • Yang, C. P. & Chen, W. T. (1993). Macromolecules, 26, 4865–4871.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography