1,2-Bis(4-amino­phen­oxy)ethane

Butt, M.S.; Akhter, Z.; Bolte, M.; Siddiqi, H.M.

doi:10.1107/S1600536808014736

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1122

doi:10.1107/S1600536808014736

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1,2-Bis(4-aminophenoxy)ethane

M. Saeed Butt,^a Zareen Akhter,^a ^* Michael Bolte ^b and Humaira M. Siddiqi ^a

^aDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan, and ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: zareenakhter@yahoo.com

(Received 12 April 2008; accepted 15 May 2008; online 21 May 2008)

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 ); Eastmond & Paprotny (1999 ); Hsio et al. (1997 ); Liaw & Liaw (2001 ); Yang & Chen (1993 ); Hergenrother et al. (2002 ).

Experimental

Crystal data

C₁₄H₁₆N₂O₂
M_r = 244.29
Orthorhombic, P b c n
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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.119
S = 1.20
1700 reflections
95 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.93 (2)	2.53 (2)	3.4082 (18)	158.6 (18)
N1—H1B⋯N1ⁱⁱ	0.94 (4)	2.48 (4)	3.360 (3)	157 (4)
N1—H1C⋯N1ⁱⁱⁱ	0.96 (5)	2.61 (5)	3.468 (3)	148 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

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: (A) -x+2, y, -z+3/2.

1,2-Bis(4-aminophenoxy)ethane top

Crystal data top

C₁₄H₁₆N₂O₂	D_x = 1.334 Mg m⁻³
M_r = 244.29	Melting point: 179 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 14232 reflections
a = 14.2157 (9) Å	θ = 3.5–29.7°
b = 10.4608 (8) Å	µ = 0.09 mm⁻¹
c = 8.1817 (5) Å	T = 173 K
V = 1216.68 (14) Å³	Block, dark red
Z = 4	0.37 × 0.35 × 0.23 mm
F(000) = 520

Data collection top

Stoe IPDSII two-circle diffractometer	1549 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.049
Graphite monochromator	θ_max = 29.6°, θ_min = 3.5°
ω scans	h = −19→19
15103 measured reflections	k = −14→11
1700 independent reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0299P)² + 0.7945P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max < 0.001
1700 reflections	Δρ_max = 0.29 e Å⁻³
95 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (2)

Crystal data top

C₁₄H₁₆N₂O₂	V = 1216.68 (14) Å³
M_r = 244.29	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.2157 (9) Å	µ = 0.09 mm⁻¹
b = 10.4608 (8) Å	T = 173 K
c = 8.1817 (5) Å	0.37 × 0.35 × 0.23 mm

Data collection top

Stoe IPDSII two-circle diffractometer	1549 reflections with I > 2σ(I)
15103 measured reflections	R_int = 0.049
1700 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.29 e Å⁻³
1700 reflections	Δρ_min = −0.19 e Å⁻³
95 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	Occ. (<1)
O1	0.91391 (6)	0.60429 (10)	0.65677 (12)	0.0243 (3)
N1	0.52550 (9)	0.65323 (15)	0.5428 (2)	0.0332 (3)
H1A	0.5093 (15)	0.718 (2)	0.470 (3)	0.048 (6)*
H1B	0.496 (3)	0.573 (4)	0.537 (5)	0.042 (11)*	0.50
H1C	0.486 (3)	0.650 (4)	0.638 (6)	0.048 (12)*	0.50
C1	0.81695 (9)	0.61092 (12)	0.63296 (15)	0.0198 (3)
C2	0.78489 (9)	0.71034 (13)	0.53437 (17)	0.0232 (3)
H2	0.8285	0.7684	0.4872	0.028*
C3	0.68899 (10)	0.72479 (13)	0.50483 (17)	0.0239 (3)
H3	0.6678	0.7931	0.4377	0.029*
C4	0.62345 (9)	0.64020 (13)	0.57255 (17)	0.0234 (3)
C5	0.65662 (10)	0.54140 (14)	0.67195 (19)	0.0268 (3)
H5	0.6131	0.4835	0.7196	0.032*
C6	0.75275 (10)	0.52624 (13)	0.70255 (17)	0.0240 (3)
H6	0.7742	0.4586	0.7704	0.029*
C7	0.94691 (9)	0.49765 (13)	0.75075 (18)	0.0244 (3)
H7A	0.9230	0.4169	0.7033	0.029*
H7B	0.9237	0.5043	0.8645	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0192 (4)	0.0272 (5)	0.0264 (5)	−0.0010 (4)	−0.0026 (4)	0.0063 (4)
N1	0.0205 (6)	0.0377 (7)	0.0413 (8)	0.0012 (5)	−0.0023 (5)	0.0043 (6)
C1	0.0202 (6)	0.0214 (6)	0.0178 (5)	−0.0003 (5)	−0.0017 (4)	−0.0017 (5)
C2	0.0231 (6)	0.0230 (6)	0.0235 (6)	−0.0010 (5)	0.0019 (5)	0.0039 (5)
C3	0.0246 (6)	0.0239 (6)	0.0233 (6)	0.0036 (5)	−0.0001 (5)	0.0028 (5)
C4	0.0205 (6)	0.0254 (6)	0.0244 (6)	0.0005 (5)	−0.0010 (5)	−0.0028 (5)
C5	0.0228 (6)	0.0267 (6)	0.0310 (7)	−0.0048 (5)	−0.0004 (5)	0.0043 (6)
C6	0.0247 (6)	0.0223 (6)	0.0250 (6)	−0.0023 (5)	−0.0033 (5)	0.0050 (5)
C7	0.0237 (6)	0.0233 (6)	0.0261 (6)	−0.0007 (5)	−0.0050 (5)	0.0024 (5)

Geometric parameters (Å, º) top

O1—C1	1.3938 (15)	C3—C4	1.3992 (19)
O1—C7	1.4338 (16)	C3—H3	0.9500
N1—C4	1.4202 (18)	C4—C5	1.397 (2)
N1—H1A	0.93 (2)	C5—C6	1.3983 (19)
N1—H1B	0.94 (4)	C5—H5	0.9500
N1—H1C	0.96 (5)	C6—H6	0.9500
C1—C2	1.3928 (18)	C7—C7ⁱ	1.510 (2)
C1—C6	1.3935 (18)	C7—H7A	0.9900
C2—C3	1.3927 (18)	C7—H7B	0.9900
C2—H2	0.9500

C1—O1—C7	115.93 (10)	C5—C4—C3	118.27 (12)
C4—N1—H1A	115.0 (14)	C5—C4—N1	120.12 (13)
C4—N1—H1B	112 (3)	C3—C4—N1	121.61 (13)
H1A—N1—H1B	120 (3)	C4—C5—C6	121.20 (12)
C4—N1—H1C	115 (3)	C4—C5—H5	119.4
H1A—N1—H1C	114 (3)	C6—C5—H5	119.4
H1B—N1—H1C	75 (3)	C1—C6—C5	119.65 (12)
C2—C1—C6	119.80 (12)	C1—C6—H6	120.2
C2—C1—O1	116.21 (11)	C5—C6—H6	120.2
C6—C1—O1	123.98 (12)	O1—C7—C7ⁱ	108.83 (10)
C3—C2—C1	120.12 (12)	O1—C7—H7A	109.9
C3—C2—H2	119.9	C7ⁱ—C7—H7A	109.9
C1—C2—H2	119.9	O1—C7—H7B	109.9
C2—C3—C4	120.96 (12)	C7ⁱ—C7—H7B	109.9
C2—C3—H3	119.5	H7A—C7—H7B	108.3
C4—C3—H3	119.5

C7—O1—C1—C2	−176.63 (12)	C3—C4—C5—C6	−0.5 (2)
C7—O1—C1—C6	4.11 (19)	N1—C4—C5—C6	179.72 (14)
C6—C1—C2—C3	−0.3 (2)	C2—C1—C6—C5	0.4 (2)
O1—C1—C2—C3	−179.57 (12)	O1—C1—C6—C5	179.62 (13)
C1—C2—C3—C4	−0.2 (2)	C4—C5—C6—C1	0.0 (2)
C2—C3—C4—C5	0.6 (2)	C1—O1—C7—C7ⁱ	174.05 (12)
C2—C3—C4—N1	−179.62 (14)

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.93 (2)	2.53 (2)	3.4082 (18)	158.6 (18)
N1—H1B···N1ⁱⁱⁱ	0.94 (4)	2.48 (4)	3.360 (3)	157 (4)
N1—H1C···N1^iv	0.96 (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.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂O₂
M_r	244.29
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	173
a, b, c (Å)	14.2157 (9), 10.4608 (8), 8.1817 (5)
V (Å³)	1216.68 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.37 × 0.35 × 0.23

Data collection
Diffractometer	Stoe IPDSII two-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15103, 1700, 1549
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.695

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.119, 1.20
No. of reflections	1700
No. of parameters	95
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.19

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.93 (2)	2.53 (2)	3.4082 (18)	158.6 (18)
N1—H1B···N1ⁱⁱ	0.94 (4)	2.48 (4)	3.360 (3)	157 (4)
N1—H1C···N1ⁱⁱⁱ	0.96 (5)	2.61 (5)	3.468 (3)	148 (3)

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

Acknowledgements

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.

References

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