2-(3,3,4,4-Tetra­fluoro­pyrrolidin-1-yl)aniline

Abstract

In the title fluorinated pyrrolidine derivative, C₁₀H₁₀F₄N₂, the dihedral angle between the best planes of the benzene and pyrrolidine rings is 62.6 (1)°. The crystal packing features inter­molecular N—H⋯F hydrogen bonds.

Related literature

For applications of fluorinated pyrrolidine derivatives, see: Hulin et al. (2005 ▶); Kerekes et al. (2011 ▶); Marson (2005 ▶); Santora et al. (2008 ▶).

Experimental

Crystal data

• C₁₀H₁₀F₄N₂

• M _r = 234.20

• Orthorhombic,

• a = 6.791 (13) Å

• b = 8.185 (16) Å

• c = 18.66 (4) Å

• V = 1037 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.14 mm⁻¹

• T = 298 K

• 0.30 × 0.28 × 0.22 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.959, T _max = 0.970

• 6022 measured reflections

• 1342 independent reflections

• 748 reflections with I > 2σ(I)

• R _int = 0.061

Refinement

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.112

• S = 1.02

• 1342 reflections

• 153 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811030339/ld2018Isup3.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
N2—H2A⋯F1i	0.84 (5)	2.59 (5)	3.295 (8)	142 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

Fluorinated pyrrolidine derivatives have attracted much attention due to their potential applications as dipeptidyl peptidase IV inhibitors (Hulin et al., 2005), asymmetric synthesis catalysts (Marson, 2005), aurora kinase inhibitors (Kerekes et al., 2011), and H3 receptor antagonists (Santora et al., 2008). Herein, we report the crystal structure of the title compound (Fig. 1), obtained by the reaction of o-phenylenediamine with trifluoromethanesulfonic acid 2,2,3,3-tretrafluoro-1,4-butanediyl ester.

The dihedral angle between the plane of phenyl ring and the least-squares plane of pyrrolidine ring is 62.63 (14)°. The pyrrolidine ring adopts a distorted N1-envelope conformation with folding angle 40.6 (2)°. The crystal packing (Fig. 2) is characterized by intermolecular N—H···F—C bonds linking molecules in zigzag chains along b.

Experimental

A mixture of trifluoromethanesulfonic acid 2,2,3,3,-tretrafluoro-1,4-butanediyl ester(1 mmol), o-phenylenediamine (1.5 mmol), Et₃N (3 mmol) and ethanol(15 ml) was placed in a round-bottomed flask fitted with a reflux condenser, and then heated at reflux for 30 h. After cooling, the organic solvent was removed under reduced pressure and to the residue was solved in dichloromethane then washed with water, and the organic layer was dried over anhydrous Na₂SO₄. After the solvent was removed, the residue was purified by flash chromatography on silica gel to afford a purple solid (164 mg), yield 70%. Crystals suitable for X-ray structural analysis were grown from CH₃CN solution at room temperature.

Refinement

H-atoms were placed in calculated positions with C—H = 0.93 Å; the H atoms of amino group were refined freely.

Since this is a light-atom structure (it does not contain any atoms heavier than F) and since the data collection was carried out using Mo radiation, it was not possible to unambiguously determine the absolute configuration of this molecule. In the absence of significant anomalous scattering effects, Friedel pairs have been merged.

Figures

Fig. 1.

View of the title compound showing the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level.

Fig. 2.

Perspective view of the crystal packing.

Crystal data

C10H10F4N2	F(000) = 480
Mr = 234.20	Dx = 1.500 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 6.791 (13) Å	µ = 0.14 mm−1
b = 8.185 (16) Å	T = 298 K
c = 18.66 (4) Å	Block, purple
V = 1037 (3) Å3	0.30 × 0.28 × 0.22 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1342 independent reflections
Radiation source: fine-focus sealed tube	748 reflections with I > 2σ(I)
graphite	Rint = 0.061
φ and ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
Tmin = 0.959, Tmax = 0.970	k = −8→10
6022 measured reflections	l = −23→23

Refinement

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.038P)2 + 0.0935P] where P = (Fo2 + 2Fc2)/3
1342 reflections	(Δ/σ)max < 0.001
153 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

Special details

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. Since this is a light atom structure (does not contain any atoms heavier than Si) and since the data collection was carried out using Mo radiation, it is not possible to unambiguously determine the absolute configuration of this molecule.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F2	0.5502 (4)	0.9533 (4)	0.28755 (12)	0.0946 (9)
F4	0.9856 (4)	0.9465 (4)	0.22927 (13)	0.0938 (9)
F3	0.7878 (4)	1.1542 (3)	0.23004 (13)	0.0903 (9)
F1	0.7058 (4)	0.7458 (3)	0.24699 (12)	0.0897 (8)
C5	0.5124 (5)	0.9963 (4)	0.04139 (17)	0.0451 (8)
C6	0.3393 (5)	1.0854 (4)	0.02680 (18)	0.0491 (9)
C3	0.8125 (6)	1.0019 (5)	0.2037 (2)	0.0608 (10)
C2	0.6375 (6)	0.8962 (5)	0.22754 (19)	0.0595 (11)
C10	0.6062 (6)	0.9131 (5)	−0.01323 (19)	0.0575 (10)
H10	0.7199	0.8541	−0.0031	0.069*
C7	0.2663 (6)	1.0832 (5)	−0.0431 (2)	0.0605 (11)
H7	0.1501	1.1383	−0.0536	0.073*
C8	0.3635 (7)	1.0009 (5)	−0.0966 (2)	0.0688 (12)
H8	0.3133	1.0027	−0.1430	0.083*
C9	0.5346 (7)	0.9155 (5)	−0.0827 (2)	0.0716 (13)
H9	0.6004	0.8608	−0.1192	0.086*
C4	0.7993 (5)	0.9997 (5)	0.12353 (18)	0.0583 (10)
H4A	0.8623	1.0946	0.1025	0.070*
H4B	0.8569	0.9013	0.1036	0.070*
C1	0.5016 (6)	0.8845 (5)	0.16406 (19)	0.0665 (12)
H1A	0.5021	0.7752	0.1440	0.080*
H1B	0.3679	0.9136	0.1771	0.080*
N1	0.5854 (4)	1.0035 (4)	0.11341 (14)	0.0466 (7)
N2	0.2447 (6)	1.1710 (5)	0.0805 (2)	0.0653 (10)
H2A	0.312 (7)	1.201 (6)	0.116 (3)	0.091 (19)*
H2B	0.171 (9)	1.254 (9)	0.068 (3)	0.17 (3)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
F2	0.093 (2)	0.123 (2)	0.0670 (14)	0.0049 (17)	0.0166 (15)	−0.0149 (14)
F4	0.0610 (15)	0.127 (2)	0.0934 (19)	0.0073 (16)	−0.0274 (15)	0.0235 (16)
F3	0.118 (2)	0.0611 (15)	0.0915 (17)	−0.0124 (16)	−0.0215 (16)	−0.0148 (13)
F1	0.111 (2)	0.0665 (15)	0.0915 (17)	0.0003 (16)	−0.0187 (16)	0.0234 (14)
C5	0.041 (2)	0.047 (2)	0.0470 (18)	−0.0033 (19)	−0.0009 (17)	0.0050 (16)
C6	0.047 (2)	0.046 (2)	0.054 (2)	−0.0019 (18)	−0.0030 (19)	0.0006 (18)
C3	0.056 (3)	0.058 (3)	0.068 (2)	0.007 (2)	−0.016 (2)	0.004 (2)
C2	0.069 (3)	0.062 (3)	0.048 (2)	0.006 (2)	−0.002 (2)	0.008 (2)
C10	0.058 (2)	0.055 (2)	0.059 (2)	0.004 (2)	0.003 (2)	−0.0032 (19)
C7	0.057 (3)	0.061 (2)	0.064 (2)	0.000 (2)	−0.016 (2)	0.009 (2)
C8	0.090 (3)	0.069 (3)	0.047 (2)	−0.013 (3)	−0.013 (2)	0.000 (2)
C9	0.087 (4)	0.069 (3)	0.058 (3)	−0.005 (3)	0.005 (2)	−0.011 (2)
C4	0.044 (2)	0.070 (3)	0.061 (2)	−0.004 (2)	−0.0026 (19)	0.010 (2)
C1	0.064 (3)	0.074 (3)	0.061 (2)	−0.017 (2)	−0.005 (2)	0.017 (2)
N1	0.0369 (16)	0.0548 (18)	0.0480 (16)	−0.0026 (15)	−0.0024 (14)	0.0073 (15)
N2	0.052 (2)	0.073 (2)	0.071 (2)	0.011 (2)	0.001 (2)	−0.004 (2)

Geometric parameters (Å, °)

F2—C2	1.350 (5)	C7—C8	1.374 (6)
F4—C3	1.347 (5)	C7—H7	0.9300
F3—C3	1.350 (5)	C8—C9	1.380 (6)
F1—C2	1.365 (5)	C8—H8	0.9300
C5—C10	1.382 (5)	C9—H9	0.9300
C5—C6	1.409 (5)	C4—N1	1.465 (5)
C5—N1	1.434 (5)	C4—H4A	0.9700
C6—N2	1.381 (5)	C4—H4B	0.9700
C6—C7	1.395 (5)	C1—N1	1.472 (5)
C3—C4	1.498 (6)	C1—H1A	0.9700
C3—C2	1.536 (6)	C1—H1B	0.9700
C2—C1	1.505 (6)	N2—H2A	0.84 (5)
C10—C9	1.384 (6)	N2—H2B	0.87 (7)
C10—H10	0.9300
C10—C5—C6	119.8 (3)	C7—C8—C9	121.1 (4)
C10—C5—N1	123.5 (3)	C7—C8—H8	119.5
C6—C5—N1	116.6 (3)	C9—C8—H8	119.5
N2—C6—C7	121.3 (4)	C8—C9—C10	118.6 (4)
N2—C6—C5	120.7 (3)	C8—C9—H9	120.7
C7—C6—C5	118.1 (3)	C10—C9—H9	120.7
F4—C3—F3	106.8 (3)	N1—C4—C3	100.8 (3)
F4—C3—C4	113.7 (3)	N1—C4—H4A	111.6
F3—C3—C4	111.6 (3)	C3—C4—H4A	111.6
F4—C3—C2	112.5 (3)	N1—C4—H4B	111.6
F3—C3—C2	108.6 (3)	C3—C4—H4B	111.6
C4—C3—C2	103.7 (3)	H4A—C4—H4B	109.4
F2—C2—F1	103.9 (3)	N1—C1—C2	103.1 (3)
F2—C2—C1	113.9 (4)	N1—C1—H1A	111.2
F1—C2—C1	111.1 (3)	C2—C1—H1A	111.2
F2—C2—C3	112.7 (4)	N1—C1—H1B	111.2
F1—C2—C3	108.8 (3)	C2—C1—H1B	111.2
C1—C2—C3	106.4 (3)	H1A—C1—H1B	109.1
C5—C10—C9	121.5 (4)	C5—N1—C4	117.6 (3)
C5—C10—H10	119.3	C5—N1—C1	116.2 (3)
C9—C10—H10	119.3	C4—N1—C1	106.7 (3)
C8—C7—C6	121.0 (4)	C6—N2—H2A	117 (3)
C8—C7—H7	119.5	C6—N2—H2B	118 (4)
C6—C7—H7	119.5	H2A—N2—H2B	107 (5)
C10—C5—C6—N2	−179.2 (4)	C6—C7—C8—C9	1.1 (6)
N1—C5—C6—N2	−1.6 (5)	C7—C8—C9—C10	0.6 (6)
C10—C5—C6—C7	1.3 (5)	C5—C10—C9—C8	−1.3 (6)
N1—C5—C6—C7	178.9 (3)	F4—C3—C4—N1	159.5 (3)
F4—C3—C2—F2	93.9 (4)	F3—C3—C4—N1	−79.6 (4)
F3—C3—C2—F2	−24.1 (4)	C2—C3—C4—N1	37.0 (4)
C4—C3—C2—F2	−142.8 (3)	F2—C2—C1—N1	115.4 (4)
F4—C3—C2—F1	−20.8 (4)	F1—C2—C1—N1	−127.7 (4)
F3—C3—C2—F1	−138.8 (3)	C3—C2—C1—N1	−9.4 (4)
C4—C3—C2—F1	102.5 (3)	C10—C5—N1—C4	31.8 (5)
F4—C3—C2—C1	−140.6 (4)	C6—C5—N1—C4	−145.8 (4)
F3—C3—C2—C1	101.4 (4)	C10—C5—N1—C1	−96.3 (4)
C4—C3—C2—C1	−17.3 (4)	C6—C5—N1—C1	86.2 (4)
C6—C5—C10—C9	0.3 (5)	C3—C4—N1—C5	−177.7 (3)
N1—C5—C10—C9	−177.1 (4)	C3—C4—N1—C1	−45.2 (4)
N2—C6—C7—C8	178.5 (4)	C2—C1—N1—C5	167.3 (3)
C5—C6—C7—C8	−2.0 (6)	C2—C1—N1—C4	34.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···F1i	0.84 (5)	2.59 (5)	3.295 (8)	142 (4)

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