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

Nawaz, H.; Akhter, Z.; Bolte, M.; Siddiqui, H.M.

doi:10.1107/S1600536809020121

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1460

doi:10.1107/S1600536809020121

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

Haq Nawaz,^a Zareen Akhter,^a ^* Michael Bolte ^b and Humaira M. Siddiqui ^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 May 2009; accepted 26 May 2009; online 6 June 2009)

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, P c a 2₁
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[F² > 2σ(F²)] = 0.037
wR(F²) = 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

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)
Symmetry codes: (i) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+1, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+2, z]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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).

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are drawn at the 50% probability level.

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

Crystal data top

C₂₇H₂₀F₆N₂O₂	D_x = 1.480 Mg m⁻³
M_r = 518.45	Melting point: 428(2) K
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 6984 reflections
a = 11.6914 (12) Å	θ = 2.4–27.8°
b = 25.641 (2) Å	µ = 0.13 mm⁻¹
c = 7.7625 (7) Å	T = 173 K
V = 2327.0 (4) Å³	Plate, colourless
Z = 4	0.28 × 0.13 × 0.08 mm
F(000) = 1064

Data collection top

Stoe IPDSII two-circle diffractometer	2186 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
Graphite monochromator	θ_max = 27.6°, θ_min = 3.0°
ω scans	h = −14→15
8855 measured reflections	k = −31→33
2875 independent reflections	l = −7→10

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0536P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
2875 reflections	Δρ_max = 0.20 e Å⁻³
351 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0185 (15)

Crystal data top

C₂₇H₂₀F₆N₂O₂	V = 2327.0 (4) Å³
M_r = 518.45	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 11.6914 (12) Å	µ = 0.13 mm⁻¹
b = 25.641 (2) Å	T = 173 K
c = 7.7625 (7) Å	0.28 × 0.13 × 0.08 mm

Data collection top

Stoe IPDSII two-circle diffractometer	2186 reflections with I > 2σ(I)
8855 measured reflections	R_int = 0.053
2875 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	Δρ_max = 0.20 e Å⁻³
2875 reflections	Δρ_min = −0.18 e Å⁻³
351 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
O1	0.51023 (15)	0.60137 (7)	0.7563 (3)	0.0351 (4)
O2	0.3320 (2)	0.94336 (7)	0.4375 (3)	0.0535 (6)
N1	0.2707 (2)	0.41299 (10)	0.7968 (4)	0.0497 (7)
H1A	0.294 (4)	0.3848 (16)	0.709 (8)	0.092 (14)*
H1B	0.194 (3)	0.4165 (13)	0.818 (5)	0.055 (10)*
N2	0.3956 (4)	1.14019 (12)	0.1429 (6)	0.0689 (10)
H2A	0.476 (5)	1.151 (2)	0.154 (9)	0.112 (19)*
H2B	0.351 (7)	1.149 (3)	0.059 (14)	0.19 (4)*
C1	0.4885 (2)	0.74565 (9)	0.1928 (4)	0.0310 (5)
C2	0.6084 (2)	0.74418 (10)	0.1076 (4)	0.0362 (6)
C3	0.3992 (2)	0.73222 (11)	0.0522 (4)	0.0359 (6)
F1	0.64236 (14)	0.69487 (6)	0.0771 (3)	0.0469 (4)
F2	0.68741 (13)	0.76594 (7)	0.2095 (3)	0.0481 (4)
F3	0.61416 (15)	0.76919 (6)	−0.0438 (2)	0.0451 (4)
F4	0.29427 (12)	0.72737 (6)	0.1216 (2)	0.0419 (4)
F5	0.39137 (15)	0.76959 (6)	−0.0682 (2)	0.0456 (4)
F6	0.42137 (14)	0.68753 (6)	−0.0311 (2)	0.0443 (4)
C11	0.4892 (2)	0.70497 (9)	0.3394 (3)	0.0300 (5)
C12	0.4286 (2)	0.65785 (10)	0.3360 (4)	0.0344 (6)
H12	0.3832	0.6497	0.2382	0.041*
C13	0.4334 (2)	0.62297 (10)	0.4718 (4)	0.0338 (6)
H13	0.3908	0.5914	0.4670	0.041*
C14	0.5001 (2)	0.63392 (10)	0.6149 (4)	0.0312 (5)
C15	0.5622 (2)	0.68025 (10)	0.6214 (4)	0.0337 (5)
H15	0.6091	0.6878	0.7182	0.040*
C16	0.5553 (2)	0.71515 (10)	0.4866 (4)	0.0333 (5)
H16	0.5965	0.7470	0.4935	0.040*
C21	0.4462 (2)	0.55454 (9)	0.7554 (4)	0.0324 (5)
C22	0.4912 (2)	0.51051 (10)	0.6797 (4)	0.0350 (6)
H22	0.5622	0.5120	0.6205	0.042*
C23	0.4310 (2)	0.46357 (10)	0.6910 (4)	0.0368 (6)
H23	0.4615	0.4331	0.6389	0.044*
C24	0.3270 (2)	0.46080 (10)	0.7774 (4)	0.0353 (6)
C25	0.2831 (2)	0.50635 (10)	0.8518 (4)	0.0352 (6)
H25	0.2119	0.5052	0.9104	0.042*
C26	0.3422 (2)	0.55313 (10)	0.8411 (4)	0.0346 (6)
H26	0.3118	0.5839	0.8919	0.042*
C31	0.4565 (2)	0.80045 (10)	0.2600 (4)	0.0328 (5)
C32	0.4944 (2)	0.84636 (10)	0.1832 (4)	0.0398 (6)
H32	0.5476	0.8446	0.0908	0.048*
C33	0.4555 (3)	0.89490 (10)	0.2398 (4)	0.0433 (7)
H33	0.4831	0.9260	0.1876	0.052*
C34	0.3765 (3)	0.89754 (11)	0.3727 (4)	0.0400 (6)
C35	0.3361 (2)	0.85234 (11)	0.4487 (4)	0.0424 (7)
H35	0.2808	0.8541	0.5381	0.051*
C36	0.3769 (2)	0.80464 (11)	0.3932 (4)	0.0372 (6)
H36	0.3499	0.7738	0.4473	0.045*
C41	0.3554 (3)	0.99075 (10)	0.3522 (4)	0.0415 (7)
C42	0.2705 (3)	1.01213 (11)	0.2503 (4)	0.0463 (7)
H42	0.2021	0.9932	0.2290	0.056*
C43	0.2852 (3)	1.06081 (11)	0.1800 (5)	0.0475 (7)
H43	0.2264	1.0754	0.1107	0.057*
C44	0.3851 (3)	1.08902 (11)	0.2087 (5)	0.0465 (7)
C45	0.4708 (3)	1.06653 (12)	0.3094 (4)	0.0468 (8)
H45	0.5401	1.0850	0.3287	0.056*
C46	0.4560 (3)	1.01741 (12)	0.3816 (4)	0.0449 (7)
H46	0.5145	1.0024	0.4505	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0375 (9)	0.0326 (9)	0.0351 (10)	−0.0058 (7)	−0.0020 (8)	0.0054 (8)
O2	0.0792 (15)	0.0282 (10)	0.0530 (14)	0.0055 (10)	0.0246 (12)	0.0000 (10)
N1	0.0423 (14)	0.0346 (12)	0.072 (2)	−0.0096 (11)	0.0017 (13)	0.0036 (13)
N2	0.086 (2)	0.0347 (14)	0.086 (3)	0.0048 (15)	0.023 (2)	0.0115 (15)
C1	0.0305 (12)	0.0283 (12)	0.0343 (13)	0.0002 (9)	0.0009 (11)	−0.0001 (12)
C2	0.0378 (13)	0.0338 (13)	0.0371 (14)	0.0017 (11)	0.0025 (12)	0.0031 (13)
C3	0.0374 (13)	0.0331 (14)	0.0373 (14)	0.0044 (11)	−0.0001 (12)	0.0043 (12)
F1	0.0455 (9)	0.0371 (8)	0.0581 (11)	0.0115 (7)	0.0114 (8)	0.0019 (8)
F2	0.0327 (8)	0.0585 (11)	0.0532 (10)	−0.0074 (7)	0.0024 (8)	0.0000 (9)
F3	0.0476 (9)	0.0453 (9)	0.0424 (9)	0.0053 (7)	0.0136 (8)	0.0067 (8)
F4	0.0317 (7)	0.0452 (9)	0.0489 (10)	0.0001 (6)	−0.0052 (8)	0.0057 (8)
F5	0.0510 (10)	0.0442 (9)	0.0416 (10)	0.0014 (7)	−0.0083 (8)	0.0118 (8)
F6	0.0540 (10)	0.0379 (8)	0.0409 (9)	0.0024 (7)	−0.0053 (8)	−0.0070 (8)
C11	0.0305 (11)	0.0263 (12)	0.0333 (14)	0.0002 (9)	0.0006 (11)	0.0016 (11)
C12	0.0351 (12)	0.0307 (13)	0.0374 (15)	−0.0018 (10)	−0.0062 (11)	−0.0007 (12)
C13	0.0337 (13)	0.0286 (12)	0.0392 (15)	−0.0045 (11)	−0.0032 (12)	0.0020 (12)
C14	0.0305 (11)	0.0292 (12)	0.0339 (13)	0.0020 (10)	0.0017 (11)	0.0030 (11)
C15	0.0344 (12)	0.0325 (13)	0.0342 (13)	−0.0036 (10)	−0.0009 (12)	−0.0026 (11)
C16	0.0359 (13)	0.0277 (11)	0.0364 (14)	−0.0029 (10)	−0.0019 (12)	−0.0021 (11)
C21	0.0324 (12)	0.0298 (12)	0.0349 (14)	−0.0020 (10)	−0.0028 (11)	0.0051 (11)
C22	0.0338 (12)	0.0374 (14)	0.0339 (14)	0.0034 (10)	0.0034 (11)	0.0018 (12)
C23	0.0385 (13)	0.0310 (12)	0.0410 (15)	0.0042 (11)	−0.0003 (12)	0.0007 (13)
C24	0.0331 (12)	0.0325 (13)	0.0404 (15)	−0.0033 (11)	−0.0067 (12)	0.0045 (12)
C25	0.0304 (12)	0.0370 (13)	0.0383 (15)	0.0001 (10)	0.0031 (12)	0.0028 (12)
C26	0.0348 (12)	0.0323 (13)	0.0368 (15)	0.0029 (11)	0.0025 (11)	0.0028 (12)
C31	0.0324 (12)	0.0303 (12)	0.0357 (14)	0.0001 (10)	0.0019 (11)	0.0026 (12)
C32	0.0472 (14)	0.0330 (13)	0.0393 (15)	−0.0003 (11)	0.0110 (13)	0.0012 (13)
C33	0.0589 (17)	0.0275 (13)	0.0435 (17)	−0.0018 (12)	0.0133 (15)	0.0013 (12)
C34	0.0516 (16)	0.0305 (13)	0.0379 (15)	0.0050 (12)	0.0073 (14)	−0.0039 (12)
C35	0.0427 (15)	0.0374 (15)	0.0472 (17)	0.0011 (12)	0.0141 (14)	0.0002 (14)
C36	0.0361 (13)	0.0310 (13)	0.0446 (16)	0.0005 (11)	0.0089 (12)	0.0022 (12)
C41	0.0557 (16)	0.0294 (13)	0.0393 (16)	0.0005 (12)	0.0093 (14)	−0.0019 (13)
C42	0.0504 (17)	0.0419 (15)	0.0466 (18)	−0.0015 (13)	−0.0028 (15)	−0.0074 (14)
C43	0.0514 (17)	0.0450 (16)	0.0460 (18)	0.0069 (13)	−0.0021 (15)	0.0023 (15)
C44	0.0630 (18)	0.0306 (13)	0.0460 (17)	0.0040 (13)	0.0134 (16)	−0.0006 (14)
C45	0.0468 (16)	0.0398 (15)	0.054 (2)	−0.0033 (13)	0.0049 (14)	−0.0118 (14)
C46	0.0455 (15)	0.0452 (16)	0.0438 (17)	0.0068 (13)	0.0022 (14)	−0.0042 (14)

Geometric parameters (Å, º) top

O1—C14	1.384 (3)	C21—C22	1.377 (4)
O1—C21	1.415 (3)	C21—C26	1.386 (4)
O2—C34	1.380 (3)	C22—C23	1.397 (4)
O2—C41	1.411 (3)	C22—H22	0.9500
N1—C24	1.400 (3)	C23—C24	1.390 (4)
N1—H1A	1.03 (5)	C23—H23	0.9500
N1—H1B	0.92 (3)	C24—C25	1.400 (4)
N2—C44	1.413 (4)	C25—C26	1.387 (4)
N2—H2A	0.99 (6)	C25—H25	0.9500
N2—H2B	0.86 (9)	C26—H26	0.9500
C1—C11	1.544 (3)	C31—C32	1.392 (4)
C1—C31	1.545 (3)	C31—C36	1.396 (4)
C1—C3	1.548 (4)	C32—C33	1.396 (4)
C1—C2	1.551 (3)	C32—H32	0.9500
C2—F2	1.338 (3)	C33—C34	1.386 (4)
C2—F3	1.340 (3)	C33—H33	0.9500
C2—F1	1.346 (3)	C34—C35	1.384 (4)
C3—F6	1.341 (3)	C35—C36	1.382 (4)
C3—F5	1.342 (3)	C35—H35	0.9500
C3—F4	1.346 (3)	C36—H36	0.9500
C11—C12	1.401 (3)	C41—C46	1.379 (4)
C11—C16	1.404 (4)	C41—C42	1.383 (5)
C12—C13	1.384 (4)	C42—C43	1.373 (4)
C12—H12	0.9500	C42—H42	0.9500
C13—C14	1.386 (4)	C43—C44	1.391 (4)
C13—H13	0.9500	C43—H43	0.9500
C14—C15	1.393 (3)	C44—C45	1.396 (5)
C15—C16	1.379 (4)	C45—C46	1.390 (4)
C15—H15	0.9500	C45—H45	0.9500
C16—H16	0.9500	C46—H46	0.9500

C14—O1—C21	117.6 (2)	C23—C22—H22	120.4
C34—O2—C41	119.3 (2)	C24—C23—C22	121.0 (2)
C24—N1—H1A	115 (3)	C24—C23—H23	119.5
C24—N1—H1B	113 (2)	C22—C23—H23	119.5
H1A—N1—H1B	116 (3)	C23—C24—N1	120.5 (3)
C44—N2—H2A	108 (3)	C23—C24—C25	118.5 (2)
C44—N2—H2B	118 (5)	N1—C24—C25	120.9 (3)
H2A—N2—H2B	124 (6)	C26—C25—C24	121.0 (2)
C11—C1—C31	111.5 (2)	C26—C25—H25	119.5
C11—C1—C3	111.9 (2)	C24—C25—H25	119.5
C31—C1—C3	106.1 (2)	C21—C26—C25	119.2 (2)
C11—C1—C2	107.1 (2)	C21—C26—H26	120.4
C31—C1—C2	112.6 (2)	C25—C26—H26	120.4
C3—C1—C2	107.7 (2)	C32—C31—C36	117.7 (2)
F2—C2—F3	106.5 (2)	C32—C31—C1	123.2 (2)
F2—C2—F1	107.0 (2)	C36—C31—C1	118.8 (2)
F3—C2—F1	106.3 (2)	C31—C32—C33	121.0 (3)
F2—C2—C1	111.2 (2)	C31—C32—H32	119.5
F3—C2—C1	114.0 (2)	C33—C32—H32	119.5
F1—C2—C1	111.4 (2)	C34—C33—C32	119.7 (3)
F6—C3—F5	106.7 (2)	C34—C33—H33	120.2
F6—C3—F4	106.9 (2)	C32—C33—H33	120.2
F5—C3—F4	106.4 (2)	O2—C34—C35	115.4 (3)
F6—C3—C1	113.6 (2)	O2—C34—C33	124.3 (3)
F5—C3—C1	112.2 (2)	C35—C34—C33	120.2 (3)
F4—C3—C1	110.7 (2)	C36—C35—C34	119.4 (3)
C12—C11—C16	117.0 (2)	C36—C35—H35	120.3
C12—C11—C1	124.5 (2)	C34—C35—H35	120.3
C16—C11—C1	118.5 (2)	C35—C36—C31	122.0 (3)
C13—C12—C11	121.5 (2)	C35—C36—H36	119.0
C13—C12—H12	119.3	C31—C36—H36	119.0
C11—C12—H12	119.3	C46—C41—C42	120.7 (3)
C12—C13—C14	120.2 (2)	C46—C41—O2	121.0 (3)
C12—C13—H13	119.9	C42—C41—O2	118.1 (3)
C14—C13—H13	119.9	C43—C42—C41	119.9 (3)
O1—C14—C13	124.2 (2)	C43—C42—H42	120.1
O1—C14—C15	116.2 (2)	C41—C42—H42	120.1
C13—C14—C15	119.7 (2)	C42—C43—C44	120.9 (3)
C16—C15—C14	119.7 (3)	C42—C43—H43	119.5
C16—C15—H15	120.2	C44—C43—H43	119.5
C14—C15—H15	120.2	C43—C44—C45	118.5 (3)
C15—C16—C11	122.0 (2)	C43—C44—N2	119.8 (3)
C15—C16—H16	119.0	C45—C44—N2	121.6 (3)
C11—C16—H16	119.0	C46—C45—C44	120.7 (3)
C22—C21—C26	121.2 (2)	C46—C45—H45	119.6
C22—C21—O1	119.7 (2)	C44—C45—H45	119.6
C26—C21—O1	118.9 (2)	C41—C46—C45	119.3 (3)
C21—C22—C23	119.1 (2)	C41—C46—H46	120.4
C21—C22—H22	120.4	C45—C46—H46	120.4

C11—C1—C2—F2	−72.8 (3)	O1—C21—C22—C23	175.2 (3)
C31—C1—C2—F2	50.2 (3)	C21—C22—C23—C24	−0.1 (4)
C3—C1—C2—F2	166.8 (2)	C22—C23—C24—N1	−176.2 (3)
C11—C1—C2—F3	166.8 (2)	C22—C23—C24—C25	0.6 (4)
C31—C1—C2—F3	−70.3 (3)	C23—C24—C25—C26	−0.6 (4)
C3—C1—C2—F3	46.3 (3)	N1—C24—C25—C26	176.2 (3)
C11—C1—C2—F1	46.5 (3)	C22—C21—C26—C25	0.6 (4)
C31—C1—C2—F1	169.4 (2)	O1—C21—C26—C25	−175.2 (3)
C3—C1—C2—F1	−74.0 (3)	C24—C25—C26—C21	0.0 (4)
C11—C1—C3—F6	−64.1 (3)	C11—C1—C31—C32	151.6 (3)
C31—C1—C3—F6	174.1 (2)	C3—C1—C31—C32	−86.4 (3)
C2—C1—C3—F6	53.3 (3)	C2—C1—C31—C32	31.2 (4)
C11—C1—C3—F5	174.8 (2)	C11—C1—C31—C36	−35.1 (3)
C31—C1—C3—F5	52.9 (3)	C3—C1—C31—C36	87.0 (3)
C2—C1—C3—F5	−67.9 (3)	C2—C1—C31—C36	−155.4 (3)
C11—C1—C3—F4	56.1 (3)	C36—C31—C32—C33	1.1 (4)
C31—C1—C3—F4	−65.7 (3)	C1—C31—C32—C33	174.6 (3)
C2—C1—C3—F4	173.5 (2)	C31—C32—C33—C34	−1.1 (5)
C31—C1—C11—C12	127.0 (3)	C41—O2—C34—C35	−171.0 (3)
C3—C1—C11—C12	8.3 (3)	C41—O2—C34—C33	8.4 (5)
C2—C1—C11—C12	−109.4 (3)	C32—C33—C34—O2	−179.5 (3)
C31—C1—C11—C16	−53.5 (3)	C32—C33—C34—C35	−0.2 (5)
C3—C1—C11—C16	−172.2 (2)	O2—C34—C35—C36	−179.3 (3)
C2—C1—C11—C16	70.1 (3)	C33—C34—C35—C36	1.3 (5)
C16—C11—C12—C13	0.2 (4)	C34—C35—C36—C31	−1.2 (5)
C1—C11—C12—C13	179.7 (2)	C32—C31—C36—C35	0.0 (4)
C11—C12—C13—C14	−0.7 (4)	C1—C31—C36—C35	−173.7 (3)
C21—O1—C14—C13	−1.5 (4)	C34—O2—C41—C46	−83.0 (4)
C21—O1—C14—C15	178.6 (2)	C34—O2—C41—C42	102.7 (3)
C12—C13—C14—O1	−179.9 (2)	C46—C41—C42—C43	−1.2 (5)
C12—C13—C14—C15	0.1 (4)	O2—C41—C42—C43	173.1 (3)
O1—C14—C15—C16	−179.0 (2)	C41—C42—C43—C44	0.4 (5)
C13—C14—C15—C16	1.0 (4)	C42—C43—C44—C45	0.7 (5)
C14—C15—C16—C11	−1.6 (4)	C42—C43—C44—N2	−176.5 (3)
C12—C11—C16—C15	0.9 (4)	C43—C44—C45—C46	−1.0 (5)
C1—C11—C16—C15	−178.6 (2)	N2—C44—C45—C46	176.1 (3)
C14—O1—C21—C22	87.0 (3)	C42—C41—C46—C45	0.8 (5)
C14—O1—C21—C26	−97.2 (3)	O2—C41—C46—C45	−173.3 (3)
C26—C21—C22—C23	−0.5 (4)	C44—C45—C46—C41	0.3 (5)

Hydrogen-bond geometry (Å, º) top

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)

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

Experimental details

Crystal data
Chemical formula	C₂₇H₂₀F₆N₂O₂
M_r	518.45
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	173
a, b, c (Å)	11.6914 (12), 25.641 (2), 7.7625 (7)
V (Å³)	2327.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.28 × 0.13 × 0.08

Data collection
Diffractometer	Stoe IPDSII two-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8855, 2875, 2186
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.088, 0.92
No. of reflections	2875
No. of parameters	351
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

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

Hydrogen-bond geometry (Å, º) top

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)

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

Acknowledgements

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.

References

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