N2,N2,N6,N6-Tetra­kis(2,3,4,5,6-penta­fluoro­benzo­yl)pyridine-2,6-diamine

Valkonen, A.; Kolehmainen, E.; Ośmiałowski, B.

doi:10.1107/S1600536811048768

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages o3429-o3430

https://doi.org/10.1107/S1600536811048768

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N²,N²,N⁶,N⁶-Tetrakis(2,3,4,5,6-pentafluorobenzoyl)pyridine-2,6-diamine

Arto Valkonen,^a ^* Erkki Kolehmainen ^a and Borys Ośmiałowski ^b

^aUniversity of Jyväskylä, Department of Chemistry, PO Box 35, FIN-40014 Jyväskylä, Finland, and ^bUniversity of Technology and Life Sciences, Department of Chemistry, Seminaryjna 3, PL-85-326 Bydgoszcz, Poland
^*Correspondence e-mail: arto.m.valkonen@jyu.fi

(Received 14 November 2011; accepted 16 November 2011; online 25 November 2011)

The title compound, C₃₃H₃F₂₀N₃O₄, is a highly fluorinated organic imide that was isolated as an unexpected product from the reaction of 2,6-diaminopyridine with 2,3,4,5,6-pentafluorobenzoyl chloride in a 1:2 molar ratio. The molecule is located on a twofold axis and one of its symmetry-independent 2,3,4,5,6-pentafluorobenzoyl groups is disordered over two sets of sites, the occupancy of the major component being 0.773 (3). In the major component, the dihedral angle between the perfluorophenyl groups is 63.64 (10)°, and these groups form dihedral angles of 67.14 (7) and 21.1 (2)° with the pyridine core. Short intermolecular C—H⋯O and C—H⋯N contacts are found in the crystal structure.

Related literature

For preparation of 2-acylaminopyridines and their structures, see: Ośmiałowski et al. (2010a ,b ). For related structures, see: Kovalevsky et al. (1999 ).

Experimental

Crystal data

C₃₃H₃F₂₀N₃O₄
M_r = 885.38
Monoclinic, C 2/c
a = 21.2370 (5) Å
b = 6.3940 (1) Å
c = 23.1045 (5) Å
β = 100.585 (1)°
V = 3083.96 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 123 K
0.30 × 0.18 × 0.16 mm

Data collection

Bruker–Nonius KappaCCD with an APEXII detector diffractometer
7138 measured reflections
3785 independent reflections
2526 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.133
S = 1.05
3785 reflections
366 parameters
97 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N1ⁱ	0.95	2.67	3.621 (5)	180
C3—H3⋯O1ⁱ	0.95	2.52	3.318 (3)	141
Symmetry code: (i) x, y-1, z.

Data collection: COLLECT (Bruker, 2008 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811048768/gk2434sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048768/gk2434Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048768/gk2434Isup3.cml

checkCIF report

Comment top

The title compound was accidentally obtained by reaction of 2,6-diaminopyridine with two equivalents of 2,3,4,5,6-pentafluorobenzoyl chloride, while the preparation of N,N'-bis(pentafluorobenzoyl)-2,6-diaminopyridine was attempted. The reaction was carried out analogously to our previously reported preparations of 2-acylaminopyridines (Ośmiałowski et al., 2010a). Previously we have structurally characterized two related secondary amides (Ośmiałowski et al., 2010b). This title imide has not been previously reported in the literature. The crystal structure of closely related imide, N,N'-(pyridine-2,6-diyl)-bis(naphthalenedicarboximide), has been reported (Kovalevsky et al., 1999).

In the crystal molecules are located on a twofold rotation axis and one of the symmetry independent perfluorobenzoyl group is disordered over two sets of sites with different occupancies (Fig.1). The perfluorophenyl groups are twisted out of the pyridine core by 67.14 (7) and 21.1 (2) ° in the major component whereas in the minor component these angles are 67.14 (7) and 63.4 (4)°. Furthermore, the dihedral angle between perfluorophenyl - group planes is 63.64 (10) ° [the minor component 67.9 (4) °]. Mercury (Macrae et al., 2008) helped us to find a motif along [0-10] direction (Fig. 2), where the molecule is connected to the translation related one by two C—H···O contacts (Table 1). Between these molecules there is also one rather long but linear C—H···N contact. A few F···C_Ar, F···F and F···O type contacts were found, which are only slightly shorter than the sum of van der Waals radii.

Related literature top

For preparation of 2-acylaminopyridines and their structures, see: Ośmiałowski et al. (2010a,b). For related structures, see: Kovalevsky et al. (1999).

Experimental top

2,3,4,5,6-Pentafluorobenzoyl chloride (2.28 g, 10 mmol) was added dropwise to a magnetically stirred solution of 2,6-diaminopyridine (0.54 g, 5 mmol) and triethylamine (1 ml) in dry methylene chloride (6 ml) at 0 °C. Subsequently the reaction mixture was refluxed for 4 h and the solution was treated with water and extracted with CH₂Cl₂. The organic solvent of the extract was evaporated under reduced pressure and the product recrystallized from hexane/ethyl acetate (10:1) mixture. ¹H NMR (CDCl₃): δ (p.p.m.) = 8.00 (t, 1H, H4), 7.45 (d, 2H, H3). Single crystals suitable for X-ray diffraction were obtained by very slow evaporation of analytical sample from NMR-tube, where CDCl₃ was used as a solvent.

Structure description top

For preparation of 2-acylaminopyridines and their structures, see: Ośmiałowski et al. (2010a,b). For related structures, see: Kovalevsky et al. (1999).

Computing details top

Data collection: COLLECT (Bruker, 2008); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structures of the major (top) and the minor (bottom) components of the disordered title molecule showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 2. The short C—H···O/N contacts (blue dashed lines) organizing the molecules in the [0 1 0] direction. The minor component of disordered part of the molecule was removed for clarity.

N²,N²,N⁶,N⁶- Tetrakis(2,3,4,5,6-pentafluorobenzoyl)pyridine-2,6-diamine top

Crystal data top

C₃₃H₃F₂₀N₃O₄	F(000) = 1736
M_r = 885.38	D_x = 1.907 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4030 reflections
a = 21.2370 (5) Å	θ = 0.4–28.3°
b = 6.3940 (1) Å	µ = 0.21 mm⁻¹
c = 23.1045 (5) Å	T = 123 K
β = 100.585 (1)°	Block, colourless
V = 3083.96 (11) Å³	0.30 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD with an APEXII detector diffractometer	2526 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
Graphite monochromator	θ_max = 28.2°, θ_min = 1.8°
Detector resolution: 9 pixels mm^-1	h = −27→28
φ and ω scans	k = −8→8
7138 measured reflections	l = −30→30
3785 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0381P)² + 7.2159P] where P = (F_o² + 2F_c²)/3
3785 reflections	(Δ/σ)_max < 0.001
366 parameters	Δρ_max = 0.35 e Å⁻³
97 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₃₃H₃F₂₀N₃O₄	V = 3083.96 (11) Å³
M_r = 885.38	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.2370 (5) Å	µ = 0.21 mm⁻¹
b = 6.3940 (1) Å	T = 123 K
c = 23.1045 (5) Å	0.30 × 0.18 × 0.16 mm
β = 100.585 (1)°

Data collection top

Bruker–Nonius KappaCCD with an APEXII detector diffractometer	2526 reflections with I > 2σ(I)
7138 measured reflections	R_int = 0.039
3785 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	97 restraints
wR(F²) = 0.133	H-atom parameters constrained
S = 1.05	Δρ_max = 0.35 e Å⁻³
3785 reflections	Δρ_min = −0.42 e Å⁻³
366 parameters

Special details top

Experimental. ¹³C NMR (CDCl₃): δ (ppm) = 159.4, 149.1, 144.5, 142.4, 141.7, 138.7, 136.6, 123.8, 110.5.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
F1	0.86727 (7)	0.9378 (2)	0.69841 (7)	0.0376 (4)
F2	0.78577 (10)	0.8370 (3)	0.59909 (7)	0.0616 (5)
F3	0.72661 (9)	0.4583 (3)	0.58930 (7)	0.0579 (5)
F4	0.75118 (6)	0.1782 (2)	0.67885 (7)	0.0362 (4)
F5	0.82680 (7)	0.2875 (2)	0.78079 (6)	0.0345 (4)
O1	0.87489 (9)	0.8475 (3)	0.82339 (8)	0.0380 (4)
N7	0.93905 (9)	0.5589 (3)	0.82488 (9)	0.0330 (5)
N1	1.0000	0.5463 (4)	0.7500	0.0278 (6)
C2	0.97130 (10)	0.4368 (4)	0.78664 (11)	0.0303 (5)
C3	0.97017 (12)	0.2207 (4)	0.78901 (14)	0.0392 (7)
H3	0.9496	0.1495	0.8165	0.047*
C4	1.0000	0.1126 (6)	0.7500	0.0450 (11)
H4	1.0000	−0.0360	0.7500	0.054*
C8	0.88798 (11)	0.6875 (4)	0.80002 (11)	0.0295 (5)
C9	0.84960 (10)	0.6158 (4)	0.74248 (10)	0.0253 (5)
C10	0.83779 (11)	0.7515 (4)	0.69504 (11)	0.0293 (5)
C11	0.79688 (13)	0.6999 (4)	0.64361 (11)	0.0373 (6)
C12	0.76727 (13)	0.5075 (4)	0.63878 (11)	0.0368 (6)
C13	0.77919 (11)	0.3668 (4)	0.68450 (11)	0.0294 (5)
C14	0.81941 (10)	0.4222 (4)	0.73576 (10)	0.0257 (5)
O2	1.02137 (19)	0.5421 (8)	0.9007 (2)	0.0851 (16)	0.773 (2)
C15	0.9663 (3)	0.5901 (8)	0.8850 (2)	0.0484 (16)	0.773 (2)
F6	0.96821 (11)	0.9929 (4)	0.93716 (10)	0.0545 (6)	0.773 (2)
F7	0.90327 (13)	1.0815 (4)	1.02541 (11)	0.0641 (8)	0.773 (2)
F8	0.82644 (14)	0.7899 (4)	1.06022 (10)	0.0548 (7)	0.773 (2)
F9	0.81043 (14)	0.4137 (4)	1.00624 (12)	0.0565 (7)	0.773 (2)
F10	0.87435 (13)	0.3237 (4)	0.91753 (12)	0.0533 (7)	0.773 (2)
C16	0.92394 (13)	0.6546 (4)	0.92708 (10)	0.0413 (10)	0.773 (2)
C17	0.93101 (11)	0.8490 (4)	0.95442 (11)	0.0429 (9)	0.773 (2)
C18	0.89756 (12)	0.8949 (3)	0.99922 (10)	0.0451 (9)	0.773 (2)
C19	0.85705 (12)	0.7464 (4)	1.01668 (10)	0.0432 (9)	0.773 (2)
C20	0.84999 (14)	0.5520 (4)	0.98934 (13)	0.0407 (11)	0.773 (2)
C21	0.88343 (15)	0.5061 (3)	0.94454 (13)	0.0381 (12)	0.773 (2)
O2B	1.0322 (5)	0.4514 (16)	0.8935 (5)	0.041 (3)	0.227 (2)
C15B	0.9785 (6)	0.524 (2)	0.8821 (5)	0.027 (4)	0.227 (2)
F6B	1.0454 (3)	0.7631 (12)	0.9763 (3)	0.048 (2)	0.227 (2)
F7B	0.9953 (4)	0.8597 (13)	1.0711 (3)	0.060 (2)	0.227 (2)
F8B	0.8734 (5)	0.7549 (14)	1.0761 (3)	0.059 (2)	0.227 (2)
F9B	0.8023 (5)	0.5329 (19)	0.9872 (4)	0.058 (3)	0.227 (2)
F10B	0.8522 (4)	0.4215 (13)	0.8935 (3)	0.0397 (18)	0.227 (2)
C16B	0.9465 (4)	0.6015 (14)	0.9305 (3)	0.029 (3)	0.227 (2)
C17B	0.9844 (3)	0.7046 (14)	0.9773 (3)	0.040 (2)	0.227 (2)
C18B	0.9591 (4)	0.7582 (14)	1.0267 (3)	0.043 (3)	0.227 (2)
C19B	0.8959 (4)	0.7086 (15)	1.0293 (3)	0.042 (3)	0.227 (2)
C20B	0.8581 (3)	0.6055 (17)	0.9825 (4)	0.034 (3)	0.227 (2)
C21B	0.8833 (4)	0.5519 (16)	0.9331 (4)	0.025 (3)	0.227 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0398 (8)	0.0247 (7)	0.0498 (9)	−0.0086 (6)	0.0121 (7)	0.0033 (7)
F2	0.0912 (14)	0.0489 (11)	0.0402 (9)	−0.0188 (10)	0.0006 (9)	0.0136 (8)
F3	0.0692 (12)	0.0568 (12)	0.0403 (9)	−0.0210 (10)	−0.0093 (8)	−0.0015 (9)
F4	0.0296 (7)	0.0285 (8)	0.0512 (9)	−0.0101 (6)	0.0095 (6)	−0.0078 (7)
F5	0.0346 (7)	0.0277 (8)	0.0409 (8)	−0.0072 (6)	0.0062 (6)	0.0061 (6)
O1	0.0464 (11)	0.0271 (9)	0.0434 (10)	−0.0083 (8)	0.0159 (8)	−0.0102 (8)
N7	0.0269 (10)	0.0343 (12)	0.0373 (11)	−0.0054 (9)	0.0049 (9)	−0.0024 (10)
N1	0.0174 (12)	0.0214 (14)	0.0433 (17)	0.000	0.0021 (12)	0.000
C2	0.0179 (10)	0.0263 (12)	0.0447 (14)	−0.0012 (10)	0.0000 (10)	0.0012 (11)
C3	0.0236 (12)	0.0271 (13)	0.0656 (19)	−0.0033 (10)	0.0042 (12)	0.0084 (13)
C4	0.0240 (17)	0.0192 (17)	0.089 (3)	0.000	0.0020 (19)	0.000
C8	0.0276 (11)	0.0245 (12)	0.0386 (13)	−0.0081 (10)	0.0118 (10)	−0.0014 (11)
C9	0.0219 (10)	0.0237 (11)	0.0331 (12)	−0.0003 (9)	0.0118 (9)	−0.0031 (10)
C10	0.0304 (12)	0.0201 (11)	0.0400 (14)	−0.0056 (10)	0.0140 (11)	−0.0031 (11)
C11	0.0457 (15)	0.0356 (15)	0.0319 (13)	−0.0049 (12)	0.0105 (11)	0.0059 (12)
C12	0.0383 (14)	0.0381 (15)	0.0329 (13)	−0.0081 (12)	0.0033 (11)	−0.0051 (12)
C13	0.0256 (11)	0.0241 (12)	0.0408 (14)	−0.0059 (10)	0.0121 (10)	−0.0057 (11)
C14	0.0228 (10)	0.0230 (12)	0.0330 (12)	0.0016 (9)	0.0095 (9)	−0.0003 (10)
O2	0.040 (2)	0.106 (4)	0.094 (3)	0.032 (2)	−0.0279 (18)	−0.061 (3)
C15	0.035 (2)	0.041 (3)	0.062 (3)	0.009 (2)	−0.011 (2)	−0.026 (2)
F6	0.0586 (14)	0.0444 (14)	0.0607 (15)	−0.0048 (12)	0.0116 (12)	−0.0191 (12)
F7	0.0776 (17)	0.0436 (14)	0.0734 (17)	−0.0001 (13)	0.0204 (13)	−0.0319 (13)
F8	0.0691 (17)	0.0515 (15)	0.0451 (13)	0.0136 (13)	0.0142 (12)	−0.0149 (11)
F9	0.0761 (18)	0.0438 (16)	0.0508 (16)	0.0007 (15)	0.0151 (14)	−0.0041 (13)
F10	0.0680 (17)	0.0360 (14)	0.0561 (16)	0.0013 (12)	0.0117 (13)	−0.0186 (12)
C16	0.038 (2)	0.036 (2)	0.043 (2)	0.0126 (18)	−0.0102 (16)	−0.0140 (17)
C17	0.0409 (18)	0.0379 (19)	0.045 (2)	0.0075 (16)	−0.0048 (16)	−0.0116 (17)
C18	0.050 (2)	0.0365 (19)	0.044 (2)	0.0138 (17)	−0.0044 (16)	−0.0166 (17)
C19	0.047 (2)	0.044 (2)	0.0341 (18)	0.0151 (18)	−0.0019 (16)	−0.0082 (17)
C20	0.055 (3)	0.029 (2)	0.033 (2)	0.0114 (19)	−0.006 (2)	−0.0009 (18)
C21	0.048 (2)	0.023 (2)	0.037 (2)	0.0125 (17)	−0.0080 (18)	−0.0023 (18)
O2B	0.040 (5)	0.030 (5)	0.044 (5)	0.004 (4)	−0.016 (4)	0.017 (4)
C15B	0.030 (8)	0.027 (8)	0.024 (6)	−0.005 (6)	0.005 (5)	0.009 (6)
F6B	0.048 (4)	0.050 (5)	0.040 (4)	−0.003 (4)	−0.007 (3)	0.011 (4)
F7B	0.083 (6)	0.049 (5)	0.038 (4)	0.001 (5)	−0.012 (4)	−0.003 (4)
F8B	0.077 (6)	0.065 (6)	0.038 (4)	0.022 (5)	0.020 (4)	−0.007 (4)
F9B	0.067 (6)	0.076 (7)	0.036 (5)	−0.012 (6)	0.018 (4)	−0.005 (5)
F10B	0.055 (5)	0.038 (4)	0.025 (3)	−0.013 (4)	0.004 (3)	−0.006 (3)
C16B	0.042 (6)	0.023 (5)	0.020 (4)	0.001 (5)	0.002 (4)	0.000 (4)
C17B	0.053 (6)	0.031 (5)	0.032 (5)	−0.001 (5)	0.000 (4)	0.003 (4)
C18B	0.060 (6)	0.039 (5)	0.027 (5)	0.007 (5)	−0.001 (5)	−0.002 (4)
C19B	0.059 (6)	0.045 (6)	0.024 (5)	0.006 (5)	0.015 (5)	−0.001 (4)
C20B	0.046 (6)	0.021 (5)	0.037 (5)	0.005 (5)	0.009 (5)	0.014 (5)
C21B	0.044 (6)	0.009 (4)	0.020 (5)	0.003 (4)	0.001 (4)	0.002 (4)

Geometric parameters (Å, º) top

F1—C10	1.341 (3)	C15—C16	1.498 (6)
F2—C11	1.339 (3)	F6—C17	1.321 (3)
F3—C12	1.338 (3)	F7—C18	1.333 (3)
F4—C13	1.340 (3)	F8—C19	1.324 (3)
F5—C14	1.338 (3)	F9—C20	1.327 (4)
O1—C8	1.213 (3)	F10—C21	1.320 (3)
N7—C8	1.398 (3)	C16—C17	1.3900
N7—C15	1.417 (6)	C16—C21	1.3900
N7—C2	1.443 (3)	C17—C18	1.3900
N7—C15B	1.446 (12)	C18—C19	1.3900
N1—C2ⁱ	1.330 (3)	C19—C20	1.3900
N1—C2	1.330 (3)	C20—C21	1.3900
C2—C3	1.383 (4)	O2B—C15B	1.215 (14)
C3—C4	1.379 (3)	C15B—C16B	1.497 (13)
C3—H3	0.9500	F6B—C17B	1.353 (9)
C4—C3ⁱ	1.379 (3)	F7B—C18B	1.332 (10)
C4—H4	0.9500	F8B—C19B	1.294 (9)
C8—C9	1.498 (3)	F9B—C20B	1.294 (12)
C9—C10	1.384 (3)	F10B—C21B	1.321 (9)
C9—C14	1.389 (3)	C16B—C17B	1.3900
C10—C11	1.377 (4)	C16B—C21B	1.3900
C11—C12	1.377 (4)	C17B—C18B	1.3900
C12—C13	1.375 (4)	C18B—C19B	1.3900
C13—C14	1.374 (3)	C19B—C20B	1.3900
O2—C15	1.200 (6)	C20B—C21B	1.3900

C8—N7—C15	117.8 (3)	C17—C16—C21	120.0
C8—N7—C2	119.1 (2)	C17—C16—C15	120.9 (3)
C15—N7—C2	121.5 (3)	C21—C16—C15	118.5 (3)
C8—N7—C15B	138.0 (6)	F6—C17—C16	120.4 (2)
C2—N7—C15B	102.4 (6)	F6—C17—C18	119.6 (2)
C2ⁱ—N1—C2	116.5 (3)	C16—C17—C18	120.0
N1—C2—C3	124.4 (3)	F7—C18—C19	119.3 (2)
N1—C2—N7	115.5 (2)	F7—C18—C17	120.7 (2)
C3—C2—N7	120.2 (2)	C19—C18—C17	120.0
C4—C3—C2	117.5 (3)	F8—C19—C18	119.6 (2)
C4—C3—H3	121.3	F8—C19—C20	120.4 (2)
C2—C3—H3	121.3	C18—C19—C20	120.0
C3—C4—C3ⁱ	119.8 (4)	F9—C20—C21	121.1 (2)
C3—C4—H4	120.1	F9—C20—C19	118.9 (2)
C3ⁱ—C4—H4	120.1	C21—C20—C19	120.0
O1—C8—N7	122.5 (2)	F10—C21—C20	119.2 (2)
O1—C8—C9	121.4 (2)	F10—C21—C16	120.7 (2)
N7—C8—C9	116.1 (2)	C20—C21—C16	120.0
C10—C9—C14	117.2 (2)	O2B—C15B—N7	128.4 (11)
C10—C9—C8	120.1 (2)	O2B—C15B—C16B	120.1 (11)
C14—C9—C8	122.4 (2)	N7—C15B—C16B	111.4 (9)
F1—C10—C11	118.5 (2)	C17B—C16B—C21B	120.0
F1—C10—C9	119.7 (2)	C17B—C16B—C15B	117.5 (7)
C11—C10—C9	121.8 (2)	C21B—C16B—C15B	122.0 (7)
F2—C11—C12	120.6 (2)	F6B—C17B—C18B	117.5 (6)
F2—C11—C10	120.0 (2)	F6B—C17B—C16B	122.5 (6)
C12—C11—C10	119.4 (2)	C18B—C17B—C16B	120.0
F3—C12—C13	120.1 (2)	F7B—C18B—C17B	119.8 (7)
F3—C12—C11	119.5 (2)	F7B—C18B—C19B	120.2 (7)
C13—C12—C11	120.4 (2)	C17B—C18B—C19B	120.0
F4—C13—C14	120.7 (2)	F8B—C19B—C20B	120.6 (8)
F4—C13—C12	119.9 (2)	F8B—C19B—C18B	119.4 (8)
C14—C13—C12	119.4 (2)	C20B—C19B—C18B	120.0
F5—C14—C13	118.0 (2)	F9B—C20B—C19B	120.8 (8)
F5—C14—C9	120.1 (2)	F9B—C20B—C21B	118.5 (8)
C13—C14—C9	121.8 (2)	C19B—C20B—C21B	120.0
O2—C15—N7	117.4 (5)	F10B—C21B—C20B	120.3 (7)
O2—C15—C16	122.8 (5)	F10B—C21B—C16B	118.6 (7)
N7—C15—C16	119.3 (4)	C20B—C21B—C16B	120.0

C2ⁱ—N1—C2—C3	0.57 (19)	C21—C16—C17—C18	0.0
C2ⁱ—N1—C2—N7	−178.4 (2)	C15—C16—C17—C18	−171.1 (3)
C8—N7—C2—N1	62.2 (3)	F6—C17—C18—F7	−0.9 (3)
C15—N7—C2—N1	−103.0 (4)	C16—C17—C18—F7	−179.2 (3)
C15B—N7—C2—N1	−111.0 (6)	F6—C17—C18—C19	178.4 (3)
C8—N7—C2—C3	−116.9 (3)	C16—C17—C18—C19	0.0
C15—N7—C2—C3	78.0 (4)	F7—C18—C19—F8	−2.2 (3)
C15B—N7—C2—C3	70.0 (6)	C17—C18—C19—F8	178.6 (3)
N1—C2—C3—C4	−1.1 (4)	F7—C18—C19—C20	179.3 (3)
N7—C2—C3—C4	177.85 (18)	C17—C18—C19—C20	0.0
C2—C3—C4—C3ⁱ	0.50 (17)	F8—C19—C20—F9	2.3 (3)
C15—N7—C8—O1	15.2 (4)	C18—C19—C20—F9	−179.1 (3)
C2—N7—C8—O1	−150.5 (2)	F8—C19—C20—C21	−178.6 (3)
C15B—N7—C8—O1	19.5 (9)	C18—C19—C20—C21	0.0
C15—N7—C8—C9	−164.5 (3)	F9—C20—C21—F10	1.7 (3)
C2—N7—C8—C9	29.8 (3)	C19—C20—C21—F10	−177.5 (3)
C15B—N7—C8—C9	−160.2 (8)	F9—C20—C21—C16	179.1 (3)
O1—C8—C9—C10	51.4 (3)	C19—C20—C21—C16	0.0
N7—C8—C9—C10	−128.9 (2)	C17—C16—C21—F10	177.4 (3)
O1—C8—C9—C14	−122.1 (3)	C15—C16—C21—F10	−11.2 (4)
N7—C8—C9—C14	57.6 (3)	C17—C16—C21—C20	0.0
C14—C9—C10—F1	−177.86 (19)	C15—C16—C21—C20	171.3 (3)
C8—C9—C10—F1	8.3 (3)	C8—N7—C15B—O2B	−155.9 (9)
C14—C9—C10—C11	1.3 (4)	C2—N7—C15B—O2B	15.1 (14)
C8—C9—C10—C11	−172.6 (2)	C8—N7—C15B—C16B	20.5 (14)
F1—C10—C11—F2	−2.1 (4)	C2—N7—C15B—C16B	−168.5 (7)
C9—C10—C11—F2	178.8 (2)	O2B—C15B—C16B—C17B	37.7 (14)
F1—C10—C11—C12	178.5 (2)	N7—C15B—C16B—C17B	−139.0 (8)
C9—C10—C11—C12	−0.6 (4)	O2B—C15B—C16B—C21B	−134.5 (10)
F2—C11—C12—F3	−0.6 (4)	N7—C15B—C16B—C21B	48.8 (11)
C10—C11—C12—F3	178.8 (3)	C21B—C16B—C17B—F6B	−177.6 (9)
F2—C11—C12—C13	179.6 (2)	C15B—C16B—C17B—F6B	10.0 (10)
C10—C11—C12—C13	−1.1 (4)	C21B—C16B—C17B—C18B	0.0
F3—C12—C13—F4	1.6 (4)	C15B—C16B—C17B—C18B	−172.3 (9)
C11—C12—C13—F4	−178.6 (2)	F6B—C17B—C18B—F7B	−1.2 (9)
F3—C12—C13—C14	−177.9 (2)	C16B—C17B—C18B—F7B	−179.0 (9)
C11—C12—C13—C14	2.0 (4)	F6B—C17B—C18B—C19B	177.8 (9)
F4—C13—C14—F5	−3.7 (3)	C16B—C17B—C18B—C19B	0.0
C12—C13—C14—F5	175.7 (2)	F7B—C18B—C19B—F8B	−2.6 (11)
F4—C13—C14—C9	179.26 (19)	C17B—C18B—C19B—F8B	178.4 (10)
C12—C13—C14—C9	−1.3 (4)	F7B—C18B—C19B—C20B	179.0 (9)
C10—C9—C14—F5	−177.3 (2)	C17B—C18B—C19B—C20B	0.0
C8—C9—C14—F5	−3.6 (3)	F8B—C19B—C20B—F9B	−7.9 (12)
C10—C9—C14—C13	−0.3 (3)	C18B—C19B—C20B—F9B	170.5 (12)
C8—C9—C14—C13	173.4 (2)	F8B—C19B—C20B—C21B	−178.4 (10)
C8—N7—C15—O2	−153.1 (5)	C18B—C19B—C20B—C21B	0.0
C2—N7—C15—O2	12.2 (7)	F9B—C20B—C21B—F10B	−3.3 (10)
C8—N7—C15—C16	34.5 (6)	C19B—C20B—C21B—F10B	167.5 (10)
C2—N7—C15—C16	−160.2 (3)	F9B—C20B—C21B—C16B	−170.7 (11)
O2—C15—C16—C17	73.5 (6)	C19B—C20B—C21B—C16B	0.0
N7—C15—C16—C17	−114.5 (4)	C17B—C16B—C21B—F10B	−167.7 (10)
O2—C15—C16—C21	−97.7 (6)	C15B—C16B—C21B—F10B	4.3 (11)
N7—C15—C16—C21	74.2 (5)	C17B—C16B—C21B—C20B	0.0
C21—C16—C17—F6	−178.4 (3)	C15B—C16B—C21B—C20B	172.0 (9)
C15—C16—C17—F6	10.5 (4)

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
C4—H4···N1ⁱⁱ	0.95	2.67	3.621 (5)	180
C3—H3···O1ⁱⁱ	0.95	2.52	3.318 (3)	141

Symmetry code: (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₃₃H₃F₂₀N₃O₄
M_r	885.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	123
a, b, c (Å)	21.2370 (5), 6.3940 (1), 23.1045 (5)
β (°)	100.585 (1)
V (Å³)	3083.96 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.30 × 0.18 × 0.16

Data collection
Diffractometer	Bruker–Nonius KappaCCD with an APEXII detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7138, 3785, 2526
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.133, 1.05
No. of reflections	3785
No. of parameters	366
No. of restraints	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.42

Computer programs: COLLECT (Bruker, 2008), DENZO-SMN (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1ⁱ	0.95	2.67	3.621 (5)	180
C3—H3···O1ⁱ	0.95	2.52	3.318 (3)	141

Symmetry code: (i) x, y−1, z.

Acknowledgements

Academy Professor Kari Rissanen and the Academy of Finland (project No. 212588) are thanked for financial support to AV. The Polish Ministry of Science and Higher Education (grant No. N N204 174138 to BO) is also gratefully acknowledged.

References

Bruker (2008). COLLECT. Bruker AXS, Delft, The Netherlands. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kovalevsky, A. Y., Shishkin, O. V. & Ponomarev, I. I. (1999). Acta Cryst. C55, 1914–1915. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ośmiałowski, B., Kolehmainen, E., Dobosz, R., Gawinecki, R., Kauppinen, R., Valkonen, A., Koivukorpi, J. & Rissanen, K. (2010a). J. Phys. Chem. A, 114, 10421–10426. Web of Science PubMed Google Scholar
Ośmiałowski, B., Kolehmainen, E., Gawinecki, R., Kauppinen, R., Koivukorpi, J. & Valkonen, A. (2010b). Struct. Chem. 21, 1061–1067. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar