3,3,4,4-Tetra­fluoro-1-[2-(3,3,4,4-tetra­fluoro­pyrrolidin-1-yl)phen­yl]pyrrolidine

Wang, J.; Zhong, J.-W.; Liu, P.-L.; Cao, W.-W.; Zeng, Z.

doi:10.1107/S1600536811033757

organic compounds

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doi:10.1107/S1600536811033757

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3,3,4,4-Tetrafluoro-1-[2-(3,3,4,4-tetrafluoropyrrolidin-1-yl)phenyl]pyrrolidine

Jin Wang,^a Jun-Wen Zhong,^a Pei-Lian Liu,^a Wan-Wan Cao ^a and Zhuo Zeng ^a,^b ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China
^*Correspondence e-mail: zhuosioc@yahoo.com.cn

(Received 6 August 2011; accepted 18 August 2011; online 27 August 2011)

The asymmetric unit of the title compound, C₁₄H₁₂F₈N₂, contains one tetrafluoropyrrolidine system and one half-molecule of benzene; the latter, together with a second heterocyclic unit, are completed by symmetry, with a twofold crystallographic axis crossing through both the middle of the bond between the C atoms bearing the heterocyclic rings and the opposite C—C bonds of the whole benzene molecule. The pyrrolidine ring shows an envelope conformation with the apex at the N atom. The dihedral angle between the least-squares plane of this ring and the benzene ring is 36.9 (5)°. There are intramolecular C—H⋯N interactions generating S(6) ring motifs. In the crystal structure, the molecules are linked by C—H⋯F interactions, forming chains parallel to [010].

Related literature

For background to the properties of fluorinated and alkyl-fluorinated heterocyclic compounds, see: Babudri et al. (2007 ). For applications of compounds with fluorinated rings, see: Brambilla (2001 ); Hagan (2008 ). For the synthesis of related compounds, see: Zeng & Shreeve (2009 ). For a description of hydrogen-bonding motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₂F₈N₂
M_r = 360.26
Orthorhombic, P b c n
a = 8.678 (3) Å
b = 9.818 (3) Å
c = 17.088 (5) Å
V = 1455.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 K
0.44 × 0.37 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.928, T_max = 0.963
6762 measured reflections
1283 independent reflections
878 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.129
S = 0.92
1283 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯F3ⁱ	0.93	2.54	3.398 (4)	154
C7—H7B⋯N1ⁱⁱ	0.97	2.45	3.020 (4)	117
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811033757/lr2025sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033757/lr2025Isup2.hkl

checkCIF report

Comment top

It is well known that the introduction of a fluorine atom or a fluoroalkyl group into heterocyclic compounds has a profound influence on their chemical, physical and biological properties (Hagan, 2008). Fluorinated ring play an important role in the pharmaceutical and advanced materials fields (Babudri et al., 2007). Many forms of systemic or topical fluoride have been studied and tested for clinical application (Brambilla, 2001). As a part of our studies in this area, we now report the synthesis and structure of the title compound.

An ORTEP view of the title compound, C₁₄H₁₂F₈N₂, is depicted in Fig. 1. The asymmetric unit contains one tetrafluoropyrrolidin system and a half-molecule of benzene. The whole molecule is generated by rotation around a 2-fold crystallographic axis crossing through, both, the middle of the bond between the carbon atoms bearing the heterocyclic rings (C3 and C3a) and the opposite C1—C1a bond. The pyrrolidine ring shows an envelope conformation with the apex at the N1 atom, the dihedral angle between the least-squares plane of this ring and the benzene moiety is 36.9 (5)°.

Intramolecular C7—H7B···N1 interactions generating S(6) ring motifs are present (Table 1). In the crystal the molecules are linked by C1—H1···F3 interactions (symmetry operation x, y - 1, z) forming chains parallel to [010] direction (Table 1 and Fig. 2).

Related literature top

For background on the properties of fluorinated and alkyl-fluorinated heterocyclic compounds, see: Babudri et al. (2007). For applications of compounds with fluorinated rings, see: Brambilla (2001); Hagan (2008). For the synthesis of related compounds, see: Zeng & Shreeve (2009). For the description of hydrogen-bonding motifs, see: Bernstein et al. (1995).

Experimental top

The compound was prepared using a slightly variation of our previously reported procedure (Zeng & Shreeve, 2009). Single crystals of the title compound were obtained by slow evaporation from dichloromethane at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP view of the title compound. Ellipsoids are drawn at the 50% probability level.
	Fig. 2. Perspective view of the crystal packing.

3,3,4,4-Tetrafluoro-1-[2-(3,3,4,4-tetrafluoropyrrolidin-1-yl)phenyl]pyrrolidine top

Crystal data top

C₁₄H₁₂F₈N₂	F(000) = 728
M_r = 360.26	D_x = 1.644 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1256 reflections
a = 8.678 (3) Å	θ = 2.4–20.4°
b = 9.818 (3) Å	µ = 0.17 mm⁻¹
c = 17.088 (5) Å	T = 293 K
V = 1455.9 (8) Å³	Block, colourless
Z = 4	0.44 × 0.37 × 0.22 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1283 independent reflections
Radiation source: fine-focus sealed tube	878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→10
T_min = 0.928, T_max = 0.963	k = −10→11
6762 measured reflections	l = −20→16

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.005P)² + 3.940P] where P = (F_o² + 2F_c²)/3
1283 reflections	(Δ/σ)_max = 0.022
109 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₄H₁₂F₈N₂	V = 1455.9 (8) Å³
M_r = 360.26	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 8.678 (3) Å	µ = 0.17 mm⁻¹
b = 9.818 (3) Å	T = 293 K
c = 17.088 (5) Å	0.44 × 0.37 × 0.22 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1283 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	878 reflections with I > 2σ(I)
T_min = 0.928, T_max = 0.963	R_int = 0.036
6762 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 0.92	Δρ_max = 0.50 e Å⁻³
1283 reflections	Δρ_min = −0.41 e Å⁻³
109 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
F1	−0.1645 (4)	−0.1228 (3)	−0.4379 (2)	0.1363 (14)
F2	0.0115 (4)	−0.1911 (3)	−0.51367 (13)	0.1146 (11)
F3	0.0249 (6)	−0.0376 (3)	−0.34538 (19)	0.181 (2)
F4	0.2023 (4)	−0.0915 (4)	−0.42295 (19)	0.1626 (19)
N1	−0.0183 (3)	−0.3376 (3)	−0.33165 (14)	0.0491 (7)
C1	−0.0181 (5)	−0.7079 (3)	−0.2889 (2)	0.0673 (11)
H1	−0.0338	−0.7897	−0.3151	0.081*
C2	−0.0311 (4)	−0.5864 (3)	−0.3283 (2)	0.0586 (10)
H2	−0.0529	−0.5872	−0.3815	0.070*
C3	−0.0126 (4)	−0.4627 (3)	−0.29036 (18)	0.0472 (8)
C4	−0.0670 (5)	−0.3406 (4)	−0.4133 (2)	0.0697 (12)
H4A	−0.1751	−0.3646	−0.4179	0.084*
H4B	−0.0060	−0.4047	−0.4434	0.084*
C5	−0.0388 (5)	−0.1976 (4)	−0.4393 (2)	0.0663 (11)
C6	0.0846 (6)	−0.1425 (4)	−0.3851 (2)	0.0743 (12)
C7	0.1226 (5)	−0.2548 (4)	−0.3301 (2)	0.0636 (10)
H7A	0.2110	−0.3065	−0.3481	0.076*
H7B	0.1432	−0.2204	−0.2779	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.089 (2)	0.106 (2)	0.214 (4)	0.0321 (19)	0.015 (2)	0.049 (2)
F2	0.171 (3)	0.124 (2)	0.0491 (14)	−0.027 (2)	0.0102 (17)	0.0096 (14)
F3	0.380 (7)	0.0575 (16)	0.106 (2)	0.053 (3)	−0.059 (3)	−0.0167 (16)
F4	0.153 (3)	0.208 (4)	0.127 (3)	−0.099 (3)	−0.046 (2)	0.102 (3)
N1	0.0642 (19)	0.0434 (14)	0.0395 (14)	−0.0035 (14)	−0.0065 (14)	0.0017 (12)
C1	0.075 (3)	0.0410 (18)	0.086 (3)	−0.005 (2)	0.006 (2)	−0.0105 (18)
C2	0.069 (3)	0.0468 (19)	0.060 (2)	−0.0026 (18)	−0.0019 (19)	−0.0090 (17)
C3	0.052 (2)	0.0416 (17)	0.0478 (17)	−0.0006 (16)	−0.0009 (16)	−0.0011 (14)
C4	0.097 (3)	0.063 (2)	0.049 (2)	−0.005 (2)	−0.020 (2)	0.0015 (19)
C5	0.084 (3)	0.069 (2)	0.047 (2)	0.009 (2)	0.003 (2)	0.0102 (18)
C6	0.107 (4)	0.058 (2)	0.058 (2)	−0.016 (2)	−0.002 (2)	0.011 (2)
C7	0.078 (3)	0.053 (2)	0.060 (2)	−0.012 (2)	−0.009 (2)	0.0106 (18)

Geometric parameters (Å, º) top

F1—C5	1.315 (5)	C2—C3	1.385 (4)
F2—C5	1.344 (4)	C2—H2	0.9300
F3—C6	1.337 (5)	C3—C3ⁱ	1.397 (6)
F4—C6	1.309 (5)	C4—C5	1.493 (5)
N1—C3	1.418 (4)	C4—H4A	0.9700
N1—C4	1.458 (4)	C4—H4B	0.9700
N1—C7	1.468 (5)	C5—C6	1.516 (6)
C1—C1ⁱ	1.364 (7)	C6—C7	1.485 (5)
C1—C2	1.374 (5)	C7—H7A	0.9700
C1—H1	0.9300	C7—H7B	0.9700

C3—N1—C4	117.9 (3)	F1—C5—F2	105.1 (3)
C3—N1—C7	116.2 (3)	F1—C5—C4	112.5 (4)
C4—N1—C7	105.7 (3)	F2—C5—C4	112.3 (3)
C1ⁱ—C1—C2	119.7 (2)	F1—C5—C6	112.0 (4)
C1ⁱ—C1—H1	120.1	F2—C5—C6	109.4 (4)
C2—C1—H1	120.1	C4—C5—C6	105.6 (3)
C1—C2—C3	121.5 (3)	F4—C6—F3	105.0 (4)
C1—C2—H2	119.3	F4—C6—C7	115.0 (4)
C3—C2—H2	119.3	F3—C6—C7	109.7 (3)
C2—C3—C3ⁱ	118.7 (2)	F4—C6—C5	112.6 (3)
C2—C3—N1	121.5 (3)	F3—C6—C5	108.2 (4)
C3ⁱ—C3—N1	119.80 (16)	C7—C6—C5	106.2 (3)
N1—C4—C5	102.6 (3)	N1—C7—C6	102.4 (3)
N1—C4—H4A	111.2	N1—C7—H7A	111.3
C5—C4—H4A	111.2	C6—C7—H7A	111.3
N1—C4—H4B	111.2	N1—C7—H7B	111.3
C5—C4—H4B	111.2	C6—C7—H7B	111.3
H4A—C4—H4B	109.2	H7A—C7—H7B	109.2

C1ⁱ—C1—C2—C3	−1.8 (8)	F2—C5—C6—F4	5.7 (5)
C1—C2—C3—C3ⁱ	−3.0 (7)	C4—C5—C6—F4	126.7 (4)
C1—C2—C3—N1	176.7 (4)	F1—C5—C6—F3	5.1 (5)
C4—N1—C3—C2	9.0 (5)	F2—C5—C6—F3	121.2 (4)
C7—N1—C3—C2	−118.0 (4)	C4—C5—C6—F3	−117.7 (4)
C4—N1—C3—C3ⁱ	−171.2 (4)	F1—C5—C6—C7	122.8 (4)
C7—N1—C3—C3ⁱ	61.8 (5)	F2—C5—C6—C7	−121.1 (4)
C3—N1—C4—C5	−172.8 (3)	C4—C5—C6—C7	0.0 (5)
C7—N1—C4—C5	−40.9 (4)	C3—N1—C7—C6	173.7 (3)
N1—C4—C5—F1	−98.1 (4)	C4—N1—C7—C6	40.8 (4)
N1—C4—C5—F2	143.5 (4)	F4—C6—C7—N1	−149.4 (4)
N1—C4—C5—C6	24.4 (4)	F3—C6—C7—N1	92.5 (4)
F1—C5—C6—F4	−110.5 (5)	C5—C6—C7—N1	−24.1 (4)

Symmetry code: (i) −x, y, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F3ⁱⁱ	0.93	2.54	3.398 (4)	154
C7—H7B···N1ⁱ	0.97	2.45	3.020 (4)	117

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂F₈N₂
M_r	360.26
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	8.678 (3), 9.818 (3), 17.088 (5)
V (Å³)	1455.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.44 × 0.37 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.928, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	6762, 1283, 878
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.129, 0.92
No. of reflections	1283
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.41

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F3ⁱ	0.93	2.54	3.398 (4)	153.7
C7—H7B···N1ⁱⁱ	0.97	2.45	3.020 (4)	117.1

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

Acknowledgements

The authors gratefully acknowledge the support of the Department of Science and Technology, Guangdong Province (grant Nos. 2010 A020507001-76, 5300410 and FIPL-05-003).

References

Babudri, F., Farinola, G. M., Naso, F. & Ragni, R. (2007). Chem. Commun. pp. 1003–1022. CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Brambilla, E. (2001). Caries Res. 35, 6–9. CrossRef CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hagan, O. D. (2008). Chem. Soc. Rev. 37, 308–319. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeng, Z. & Shreeve, J. M. (2009). J. Fluorine Chem. 130, 727–732. CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
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Volume 67| Part 9| September 2011| Page o2399

doi:10.1107/S1600536811033757

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3,3,4,4-Tetra­fluoro-1-[2-(3,3,4,4-tetra­fluoro­pyrrolidin-1-yl)phen­yl]pyrrolidine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3,3,4,4-Tetrafluoro-1-[2-(3,3,4,4-tetrafluoropyrrolidin-1-yl)phenyl]pyrrolidine