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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811022434/ng5179Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

The hydrogen atoms were placed at calculated position with C—H = 0.99 Å for CH₂ and 1.00 Å for CH. For all H atoms U_iso(H) values were fixed at 1.2U_eq of the carrier atom.

Figures

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.

Crystal data

C14H18F6N2O2	Z = 1
Mr = 360.30	F(000) = 186
Triclinic, P1	Dx = 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

Bruker APEXII CCD diffractometer	1731 independent reflections
Radiation source: fine-focus sealed tube	1586 reflections with I > 2σ(I)
graphite	Rint = 0.009
Detector resolution: 8.3 pixels mm-1	θmax = 28.6°, θmin = 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
Tmin = 0.921, Tmax = 0.962	l = −12→12
3303 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0398P)2 + 0.1258P] where P = (Fo2 + 2Fc2)/3
1731 reflections	(Δ/σ)max = 0.008
109 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.23 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.

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+2, −z+1.