1,1′-(4,4′-Bipiperidine-1,1′-di­yl)bis­(2,2,2-trifluoro­ethanone)

Yadav, V.N.; Hansen, T.; Görbitz, C.H.

doi:10.1107/S1600536811022434

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1691

doi:10.1107/S1600536811022434

Open

access

1,1′-(4,4′-Bipiperidine-1,1′-diyl)bis(2,2,2-trifluoroethanone)

Vitthal N. Yadav,^a Tore Hansen ^a and Carl Henrik Görbitz ^a ^*

^aDepartment of Chemistry, University of Oslo, Oslo, Norway
^*Correspondence e-mail: c.h.gorbitz@kjemi.uio.no

(Received 6 June 2011; accepted 9 June 2011; online 18 June 2011)

The title compound, C₁₄H₁₈F₆N₂O₂, has a central center of symmetry with both piperidine rings occurring in regular chair conformations. Even though the structure is fairly compact with no sizable voids, the shortest H⋯O distance is as long as 2.58 Å.

Related literature

For applications of and structures related to 4,4′-bipiperidine compounds, see: Medina et al. (1991 ); Li et al. (2009 ); Wang et al. (2007 ); Melchiorre et al. (2001 ); Adams et al. (2006 ); Angeloni & Orpen (2001 ); De las Casas Engel et al. (2010 ). For a related synthesis, see: Schenck et al. (2004 ). For interpretation of C—H⋯F bond configurations, see: Shimoni & Glusker (1994 ). For the use of a large specimen for data collection, see: Görbitz (1999 ).

Experimental

Crystal data

C₁₄H₁₈F₆N₂O₂
M_r = 360.30
Triclinic, $[P \overline 1]$
a = 6.6825 (12) Å
b = 6.7350 (12) Å
c = 9.3089 (16) Å
α = 99.952 (2)°
β = 108.564 (2)°
γ = 101.542 (2)°
V = 376.30 (12) Å³
Z = 1
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 105 K
1.00 × 0.50 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.921, T_max = 0.962
3303 measured reflections
1731 independent reflections
1586 reflections with I > 2σ(I)
R_int = 0.009

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.06
1731 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022434/ng5179sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022434/ng5179Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022434/ng5179Isup3.cml

checkCIF report

Comment top

The structures containing 4,4'-bipiperidine scaffold attract more interest as molecular spacer for sustaining functional diversity, which finds different applications in materials chemistry (Wang et al., 2007; Medina et al., 1991; Li et al., 2009; Adams et al., 2006; Angeloni & Orpen, 2001), Organocatalysis (De las Casas Engel et al., 2010) and pharmaceutical development (Melchiorre et al., 2001).

The asymmetric unit contain one half of the N,N'-di-trifluoroacetyl-4,4'-bipiperidine molecule. The molecular structure is shown in Fig. 1. The intermolecular interactions between –C—H···F–, –F···F–, C=O···F–, C—H ··· O=C and π ···O=C leading to the supramolecular three-dimensional crystal packing.

In the significant –C—H···F– interactions, the fluorine atom acts as an H-bond acceptor. The distances between –H···F– nearly 2.572 Å shows important and binding interactions are mainly electrostatic. The angles –C—H···F-(169.03 & 147.63 °) are linear, indicates repulsive interactions (Shimoni & Glusker, 1994).

Related literature top

For applications and related structures of 4,4'-bipiperidine compounds, see: Medina et al. (1991); Li et al. (2009); Wang et al. (2007); Melchiorre et al. (2001); Adams et al. (2006); Angeloni & Orpen (2001); De las Casas Engel et al. (2010). For a related synthesis, see: Schenck et al. (2004). For interpretation of C—H···F bond configurations, see: Shimoni & Glusker (1994). For the use of a large specimen for data collection, see: Görbitz (1999).

Experimental top

The compound (I) was prepared by the procedure reported for piperidine by Schenck et al. (2004). The 4,4'-bipiperidyl dihydrochloride (0.5 g, 2.07 mmol) and triethyl amine (1.2 ml, 8.6 mmol) mixed together at 0 °C in 20 ml of dry diethyl ether, stirred the mixture for 10 min. and added trifluoro acetic anhydride (0.61 ml, 4.3 mmol) dropwise, continued stirring at room temperature for 3 h., added 1 ml of 2M HCl and stirred for 10 min., filtered the solid residue and washed with fresh diethyl ether.

The highly stable X-ray quality crystals were obtained by slow evaporation of dichloromethane. A rather large specimen (maximum dimension 1.00 mm) was used for data collection to get high diffraction intensitites. Previous investigations indicate that this does not represent a problem for a light-atom-only structure (see Görbitz, 1999).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level; H atoms are spheres of arbitrary size.
	Fig. 2. The unit cell and three-dimensional crystal packing of (I) viewed approximately along the a-axis. Hydrogen atoms have been left out for clarity.

1,1'-(4,4'-Bipiperidine-1,1'-diyl)bis(2,2,2-trifluoroethanone) top

Crystal data top

C₁₄H₁₈F₆N₂O₂	Z = 1
M_r = 360.30	F(000) = 186
Triclinic, P1	D_x = 1.590 Mg m⁻³
Hall symbol: -P 1	Melting point: 397 K
a = 6.6825 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.7350 (12) Å	Cell parameters from 2545 reflections
c = 9.3089 (16) Å	θ = 2.4–28.3°
α = 99.952 (2)°	µ = 0.16 mm⁻¹
β = 108.564 (2)°	T = 105 K
γ = 101.542 (2)°	Rods, colourless
V = 376.30 (12) Å³	1.00 × 0.50 × 0.25 mm

Data collection top

Bruker APEXII CCD diffractometer	1731 independent reflections
Radiation source: fine-focus sealed tube	1586 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.009
Detector resolution: 8.3 pixels mm^-1	θ_max = 28.6°, θ_min = 2.4°
Sets of exposures each taken over 0.5° ω rotation scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −8→8
T_min = 0.921, T_max = 0.962	l = −12→12
3303 measured 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0398P)² + 0.1258P] where P = (F_o² + 2F_c²)/3
1731 reflections	(Δ/σ)_max = 0.008
109 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₄H₁₈F₆N₂O₂	γ = 101.542 (2)°
M_r = 360.30	V = 376.30 (12) Å³
Triclinic, P1	Z = 1
a = 6.6825 (12) Å	Mo Kα radiation
b = 6.7350 (12) Å	µ = 0.16 mm⁻¹
c = 9.3089 (16) Å	T = 105 K
α = 99.952 (2)°	1.00 × 0.50 × 0.25 mm
β = 108.564 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1731 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1586 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.962	R_int = 0.009
3303 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.06	Δρ_max = 0.39 e Å⁻³
1731 reflections	Δρ_min = −0.23 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	0.11060 (12)	0.31663 (10)	0.84127 (9)	0.03113 (19)
F2	0.00855 (11)	0.51373 (11)	0.68885 (8)	0.02834 (18)
F3	0.13374 (10)	0.63747 (10)	0.93992 (7)	0.02236 (16)
O1	0.49112 (14)	0.43556 (12)	0.82275 (10)	0.02475 (19)
N1	0.47091 (14)	0.76768 (13)	0.81595 (10)	0.01700 (19)
C2	0.68525 (17)	0.82626 (17)	0.80093 (12)	0.0199 (2)
H21	0.7640	0.7193	0.8255	0.024*
H22	0.7745	0.9622	0.8764	0.024*
C3	0.65544 (17)	0.84357 (16)	0.63442 (12)	0.0186 (2)
H31	0.5798	0.7036	0.5607	0.022*
H32	0.8014	0.8906	0.6274	0.022*
C4	0.52192 (16)	0.99793 (15)	0.58605 (11)	0.0155 (2)
H41	0.6099	1.1413	0.6534	0.019*
C5	0.30751 (16)	0.94359 (15)	0.61687 (11)	0.0166 (2)
H51	0.2321	1.0545	0.5987	0.020*
H52	0.2099	0.8101	0.5418	0.020*
C6	0.34705 (17)	0.92258 (15)	0.78370 (12)	0.0171 (2)
H61	0.4304	1.0600	0.8592	0.021*
H62	0.2047	0.8779	0.7965	0.021*
C7	0.39316 (17)	0.57031 (16)	0.82058 (11)	0.0176 (2)
C8	0.15978 (18)	0.51030 (16)	0.82412 (13)	0.0210 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0357 (4)	0.0179 (3)	0.0457 (4)	0.0046 (3)	0.0226 (3)	0.0114 (3)
F2	0.0223 (3)	0.0307 (4)	0.0252 (3)	0.0026 (3)	0.0040 (3)	0.0043 (3)
F3	0.0247 (3)	0.0240 (3)	0.0250 (3)	0.0098 (3)	0.0148 (3)	0.0082 (3)
O1	0.0318 (4)	0.0201 (4)	0.0305 (4)	0.0140 (3)	0.0164 (4)	0.0093 (3)
N1	0.0180 (4)	0.0177 (4)	0.0194 (4)	0.0078 (3)	0.0087 (3)	0.0080 (3)
C2	0.0169 (5)	0.0246 (5)	0.0218 (5)	0.0080 (4)	0.0078 (4)	0.0110 (4)
C3	0.0184 (5)	0.0217 (5)	0.0207 (5)	0.0093 (4)	0.0093 (4)	0.0095 (4)
C4	0.0164 (4)	0.0152 (4)	0.0163 (5)	0.0055 (4)	0.0065 (4)	0.0052 (4)
C5	0.0175 (5)	0.0175 (4)	0.0174 (5)	0.0073 (4)	0.0072 (4)	0.0063 (4)
C6	0.0211 (5)	0.0160 (4)	0.0185 (5)	0.0090 (4)	0.0093 (4)	0.0065 (4)
C7	0.0218 (5)	0.0174 (5)	0.0157 (4)	0.0070 (4)	0.0086 (4)	0.0043 (4)
C8	0.0238 (5)	0.0171 (5)	0.0233 (5)	0.0053 (4)	0.0103 (4)	0.0058 (4)

Geometric parameters (Å, º) top

F1—C8	1.3299 (12)	C3—H31	0.9900
F2—C8	1.3478 (13)	C3—H32	0.9900
F3—C8	1.3363 (12)	C4—C5	1.5354 (14)
O1—C7	1.2199 (13)	C4—C4ⁱ	1.5404 (19)
N1—C7	1.3403 (13)	C4—H41	1.0000
N1—C2	1.4654 (13)	C5—C6	1.5268 (13)
N1—C6	1.4694 (12)	C5—H51	0.9900
C2—C3	1.5267 (14)	C5—H52	0.9900
C2—H21	0.9900	C6—H61	0.9900
C2—H22	0.9900	C6—H62	0.9900
C3—C4	1.5352 (13)	C7—C8	1.5433 (15)

C7—N1—C2	118.28 (8)	C6—C5—C4	112.24 (8)
C7—N1—C6	127.41 (9)	C6—C5—H51	109.2
C2—N1—C6	112.38 (8)	C4—C5—H51	109.2
N1—C2—C3	110.03 (8)	C6—C5—H52	109.2
N1—C2—H21	109.7	C4—C5—H52	109.2
C3—C2—H21	109.7	H51—C5—H52	107.9
N1—C2—H22	109.7	N1—C6—C5	109.91 (8)
C3—C2—H22	109.7	N1—C6—H61	109.7
H21—C2—H22	108.2	C5—C6—H61	109.7
C2—C3—C4	111.99 (8)	N1—C6—H62	109.7
C2—C3—H31	109.2	C5—C6—H62	109.7
C4—C3—H31	109.2	H61—C6—H62	108.2
C2—C3—H32	109.2	O1—C7—N1	125.64 (10)
C4—C3—H32	109.2	O1—C7—C8	117.66 (9)
H31—C3—H32	107.9	N1—C7—C8	116.70 (9)
C5—C4—C3	109.77 (8)	F1—C8—F3	107.55 (8)
C5—C4—C4ⁱ	111.59 (10)	F1—C8—F2	107.07 (9)
C3—C4—C4ⁱ	111.60 (10)	F3—C8—F2	107.07 (9)
C5—C4—H41	107.9	F1—C8—C7	110.32 (9)
C3—C4—H41	107.9	F3—C8—C7	113.47 (9)
C4ⁱ—C4—H41	107.9	F2—C8—C7	111.08 (8)

C7—N1—C2—C3	104.98 (10)	C2—N1—C7—O1	4.65 (15)
C6—N1—C2—C3	−60.38 (11)	C6—N1—C7—O1	167.54 (10)
N1—C2—C3—C4	55.87 (11)	C2—N1—C7—C8	−175.62 (8)
C2—C3—C4—C5	−51.51 (11)	C6—N1—C7—C8	−12.72 (15)
C2—C3—C4—C4ⁱ	−175.77 (10)	O1—C7—C8—F1	4.75 (13)
C3—C4—C5—C6	51.41 (11)	N1—C7—C8—F1	−175.01 (8)
C4ⁱ—C4—C5—C6	175.67 (9)	O1—C7—C8—F3	125.51 (10)
C7—N1—C6—C5	−103.67 (11)	N1—C7—C8—F3	−54.25 (12)
C2—N1—C6—C5	60.06 (11)	O1—C7—C8—F2	−113.81 (10)
C4—C5—C6—N1	−55.39 (11)	N1—C7—C8—F2	66.43 (12)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈F₆N₂O₂
M_r	360.30
Crystal system, space group	Triclinic, P1
Temperature (K)	105
a, b, c (Å)	6.6825 (12), 6.7350 (12), 9.3089 (16)
α, β, γ (°)	99.952 (2), 108.564 (2), 101.542 (2)
V (Å³)	376.30 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	1.00 × 0.50 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.921, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	3303, 1731, 1586
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.06
No. of reflections	1731
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.23

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXTL (Sheldrick, 2008).

References

Adams, C. J., Crawford, P. C., Orpen, A. G. & Podesta, T. J. (2006). Dalton Trans. pp. 4078–4092. Web of Science CSD CrossRef PubMed Google Scholar
Angeloni, A. & Orpen, A. G. (2001). Chem. Commun. pp. 343–344. Web of Science CSD CrossRef Google Scholar
Bruker (2007). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
De las Casas Engel, T., Lora Maroto, B. & De la Moya Cerero, S. (2010). Eur. J. Org. Chem. 9, 1717–1727. CrossRef Google Scholar
Görbitz, C. H. (1999). Acta Cryst. B55, 1090–1098. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, J., Wang, G., Shi, Z., Yang, M. & Luck, R. L. (2009). Struct. Chem. 20, 869–876. CrossRef CAS Google Scholar
Medina, J., Li, C., Bott, S. G., Atwood, J. L. & Gokel, G. W. (1991). J. Am. Chem. Soc. 113, 366–361. CrossRef CAS Google Scholar
Melchiorre, C., Bolognesi, M. L., Budriesi, R., Ghelardini, C., Chiarini, A., Minarini, A., Rosini, M., Tumiatti, V. & Wade, E. J. (2001). J. Med. Chem. 44, 4035–4038. Web of Science CrossRef PubMed CAS Google Scholar
Schenck, H. A., Lenkowski, P. W., Choudhury-Mukherjee, I., Ko, S.-H., Stables, J. P., Patel, M. K. & Browna, M. L. (2004). Bioorg. Med. Chem. 12, 979–993. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shimoni, L. & Glusker, J. P. (1994). Struct. Chem. 5, 383–397. CrossRef CAS Web of Science Google Scholar
Wang, W., Yamnitz, C. R. & Gokel, G. W. (2007). Heterocycles, 73, 825–839. PubMed CAS Google Scholar