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

Arto Valkonen; Erkki Kolehmainen; Borys Ośmiałowski

doi:10.1107/S1600536811048768

. 2011 Nov 25;67(Pt 12):o3429–o3430. doi: 10.1107/S1600536811048768

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

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

PMCID: PMC3239063 PMID: 22199911

Abstract

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,
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[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 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

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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811048768/gk2434sup1.cif

e-67-o3429-sup1.cif^{(33.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048768/gk2434Isup2.hkl

e-67-o3429-Isup2.hkl^{(181.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811048768/gk2434Isup3.cml

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
C4—H4⋯N1ⁱ	0.95	2.67	3.621 (5)	180
C3—H3⋯O1ⁱ	0.95	2.52	3.318 (3)	141

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Symmetry code: (i) Inline graphic .

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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.