4,4′-[4,4′-(Perfluoro­propane-2,2-di­yl)bis­(4,1-phenyl­eneoxy)]dianiline

Haq Nawaz; Zareen Akhter; Michael Bolte; Humaira M Siddiqui

doi:10.1107/S1600536809020121

. 2009 Jun 6;65(Pt 7):o1460. doi: 10.1107/S1600536809020121

4,4′-[4,4′-(Perfluoropropane-2,2-diyl)bis(4,1-phenyleneoxy)]dianiline

Haq Nawaz ^a, Zareen Akhter ^a,^*, Michael Bolte ^b, Humaira M Siddiqui ^a

PMCID: PMC2969474 PMID: 21582764

Abstract

In the title compound, C₂₇H₂₀F₆N₂O₂, the dihedral angles between the planes of the aromatic rings connected by the ether O atoms are 84.13 (8) and 75.06 (9)°. The crystal structure is stabilized by N—H⋯O and N—H⋯F hydrogen bonds.

Related literature

For background to the properties and applications of polyimides, see: Jiang et al. (2008 ▶); Matsuura et al. (1991 ▶); Nakamura et al. (2001 ▶); Stoessel et al. (1998 ▶); Zhao et al. (2008 ▶). For related structures, see: Nawaz et al. (2008 ▶); Bocelli & Cantoni (1989 ▶).

Experimental

Crystal data

C₂₇H₂₀F₆N₂O₂
M _r = 518.45
Orthorhombic,
a = 11.6914 (12) Å
b = 25.641 (2) Å
c = 7.7625 (7) Å
V = 2327.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 173 K
0.28 × 0.13 × 0.08 mm

Data collection

Stoe IPDSII two-circle diffractometer
Absorption correction: none
8855 measured reflections
2875 independent reflections
2186 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.088
S = 0.92
2875 reflections
351 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020121/pv2158sup1.cif

e-65-o1460-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020121/pv2158Isup2.hkl

e-65-o1460-Isup2.hkl^{(141.1KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯F1ⁱ	1.03 (5)	2.41 (5)	3.404 (4)	164 (4)
N1—H1B⋯O1ⁱⁱ	0.92 (3)	2.24 (4)	3.083 (3)	151 (3)
N2—H2B⋯F2ⁱⁱⁱ	0.86 (9)	3.12 (8)	3.462 (4)	106 (7)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors are grateful to the Department of Chemistry, Quaid-I-Azam University, and the Higher Education Commission, H-9 Islamabad, Pakistan, for financial support and the Institute for Inorganic Chemistry, University of Frankfurt, Germany for providing laboratory and analytical facilities.

supplementary crystallographic information

Comment

Polyimides are well known for their excellent thermal and oxidative stability as well as their excellent mechanical properties (Stoessel et al., 1998) suited for use as matrix resins, adhesives and coatings for high-performance applications in the aerospace and electronics industries (Nakamura et al., 2001). These advantages simultaneously give rise to low solubility and poor processability, which can be overcome by incorporation of new functional groups (Matsuura et al., 1991). Many chemists have introduced CF₃ in polyimides backbone either by means of diamine or dianhydride unit to overcome the solubility issues (Zhao et al., 2008; Jiang et al., 2008). Continuing our investigations in this important area (Nawaz et al., 2008), we have prepared the title compound, (I), which is also a monomer diamine containing two CF₃ groups incorporated to enhance the solubility of the resulting polyimides.

The structure of the title compound is presented in Fig. 1. Its bond lenghts and bond angles agree with the corresponding bond lengths and bond angles reported for closely related structures (Nawaz et al., 2008; Bocelli & Cantoni, 1989. The crystal structure of the title compound is stabilized by N—H···O and N—H···F hydrogen bonds; details have been provided in Table 1.

Experimental

4,4'-(Perfluoropropane-2,2-diyl)bis((4-nitrophenoxy)benzene) (2.00 g, 3.98 mmol) was reduced to corresponding diamine using 10 mL hydrazine and 0.10 g Pd—C as catalyst in 80 mL ethanol under reflux for 24 h. The reaction mixture was filtered and solvent was evaporated to obtain the crude product. It was later recrystallized from absolute ethanol. (Yield 1.56 g; 76%, m.p = 428 (2) K).