Crystal structure of 1-(piperidin-1-yl)butane-1,3-dione

Schwierz, M.; Görls, H.; Imhof, W.

doi:10.1107/S1600536814025768

organic compounds

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Volume 70| Part 12| December 2014| Page o1297

doi:10.1107/S1600536814025768

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Crystal structure of 1-(piperidin-1-yl)butane-1,3-dione

Markus Schwierz,^a Helmar Görls ^b and Wolfgang Imhof ^a ^*

^aUniversity Koblenz-Landau, Institute for Integrated Natural Sciences, Universitätsstrasse 1, 56070 Koblenz, Germany, and ^bFriedrich-Schiller-University Jena, Institute of Inorganic and Analytical Chemistry, Humboldtstrasse 8, 07743 Jena, Germany
^*Correspondence e-mail: imhof@uni-koblenz.de

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 6 November 2014; accepted 25 November 2014; online 29 November 2014)

In the title compound, C₉H₁₅NO₂, the piperidine ring exhibits a chair conformation. The butanedione subunit exhibits a conformation with the ketone C atom in an eclipsed position with respect to the amide carbonyl group. In the crystal, a two-dimensional layered arrangement is formed by hydrogen bonds of the C—H⋯O type between the methyl group and the exocyclic methylene unit as donor sites and the amide carbonyl O atom as the acceptor of a bifurcated hydrogen bond. These layers are oriented parallel to the ab plane.

Keywords: crystal structure; 1-(piperidin-1-yl)butane-1,3-dione; weak hydrogen bonding.

CCDC reference: 1035958

1. Related literature

For the synthetic procedure, see: Sridharan et al. (2010 ). For a survey concerning weak hydrogen bonds, see: Desiraju & Steiner (1999 ).

2. Experimental

2.1. Crystal data

C₉H₁₅NO₂
M_r = 169.22
Monoclinic, P 2₁ /c
a = 5.4455 (1) Å
b = 9.1901 (2) Å
c = 17.8837 (4) Å
β = 94.506 (1)°
V = 892.22 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 133 K
0.12 × 0.09 × 0.07 mm

2.2. Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.717, T_max = 0.746
5612 measured reflections
2035 independent reflections
1777 reflections with I > 2σ(I)
R_int = 0.023

2.3. Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.14
2035 reflections
169 parameters
All H-atom parameters refined
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1ⁱ	0.96 (2)	2.459 (17)	3.378 (3)	161 (1)
C9—H9B⋯O1ⁱⁱ	0.99 (2)	2.601 (18)	3.466 (3)	146 (1)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO ; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1035958

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814025768/bg2540sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814025768/bg2540Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814025768/bg2540Isup3.cml

checkCIF report

Comment top

The title compound is an intermediate in the synthesis of 2,2-dimethoxy-1-(pyridin-2-yl)ethanone and has been synthesized from piperidine and 2,2,6-trimethyl-4H-1,3-dioxin-4-one following a modified procedure (Sridharan et al., 2010). As it is expected the piperidine ring shows a chair conformation and the amide substructure is planar. The butanedione subunit exhibits a conformation with the ketone carbon atom in an eclipsed position with respect to the amide carbonyl group (Figure 1). The dihedral angle between the two carbonyl groups therefore measures to 81.4°. In the crystal structure, a two-dimensional layered arrangement is formed by hydrogen bonds of the C–H···O type between the methyl group and the exocyclic methylene unit as donor sites and the amide carbonyl oxygen atom as the acceptor of a bifurcated hydrogen bond. These layers are oriented along to the ab plane (Figure 2).

Related literature top

For the synthetic procedure, see: Sridharan et al. (2010). For a survey concerning weak hydrogen bonds, see: Desiraju & Steiner (1999).

Experimental top

0.2 Mol of piperidine (17.0 g, 19.8 ml), 0.2 mol of sodium acetate (17.0 g) and a slight excess (0.26 mol, 37.0 g, 34.6 ml) 2,2,6-trimethyl-4H-1,3-dioxin-4-one together with 40 ml THF are refluxed for 24 h. After cooling down to room temperature the solution is filtered and the remaining sodium acetate is washed with diethylether (3 × 20 ml). The combined THF and diethylether solutions are treated with brine (3 × 25 ml) and dried with Na₂SO₄. After filtration the organic solution is evaporated to dryness. The raw product may either be purified by chromatography (silica, light petroleum: ethyl acetate = 9: 1, yield 67%) or by destillation in vacuo (0.2 mbar, yield: 83%). If only the product fraction that is condensed into a Schlenk tube which is cooled with liquid nitrogen using a bath temperature above 100°C is collected, crystalline material of the title compound suitable for X-ray crystallography is obtained.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Figure 1. Molecular structure of the title compound with thermal ellipsoids drawn at the 50% probability level.

Figure 2. Crystal structure of the title compound showing layers of molecules along the ab plane which are built up by bifurcated C–H···O hydrogen bonds.

1-(Piperidin-1-yl)butane-1,3-dione top

Crystal data top

C₉H₁₅NO₂	Z = 4
M_r = 169.22	F(000) = 368
Monoclinic, P2₁/c	D_x = 1.260 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.4455 (1) Å	µ = 0.09 mm⁻¹
b = 9.1901 (2) Å	T = 133 K
c = 17.8837 (4) Å	Prism, colourless
β = 94.506 (1)°	0.12 × 0.09 × 0.07 mm
V = 892.22 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	2035 independent reflections
Radiation source: fine-focus sealed tube	1777 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
phi– + ω–scan	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −7→6
T_min = 0.717, T_max = 0.746	k = −7→11
5612 measured reflections	l = −23→21

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.107	All H-atom parameters refined
S = 1.14	w = 1/[σ²(F_o²) + (0.041P)² + 0.4171P] where P = (F_o² + 2F_c²)/3
2035 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₁₅NO₂	V = 892.22 (3) Å³
M_r = 169.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.4455 (1) Å	µ = 0.09 mm⁻¹
b = 9.1901 (2) Å	T = 133 K
c = 17.8837 (4) Å	0.12 × 0.09 × 0.07 mm
β = 94.506 (1)°

Data collection top

Nonius KappaCCD diffractometer	2035 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	1777 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.746	R_int = 0.023
5612 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.107	All H-atom parameters refined
S = 1.14	Δρ_max = 0.31 e Å⁻³
2035 reflections	Δρ_min = −0.19 e Å⁻³
169 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
O1	0.73273 (18)	0.88779 (10)	0.27173 (5)	0.0232 (2)
O2	0.6753 (2)	0.70560 (11)	0.11035 (5)	0.0279 (3)
N1	0.5948 (2)	0.73198 (12)	0.35732 (6)	0.0202 (3)
C1	0.5498 (3)	0.84895 (15)	0.41067 (7)	0.0210 (3)
H1B	0.661 (3)	0.8308 (18)	0.4570 (9)	0.022 (4)*
H1A	0.594 (3)	0.9416 (19)	0.3881 (9)	0.023 (4)*
C2	0.2840 (3)	0.84538 (15)	0.43124 (8)	0.0236 (3)
H2B	0.257 (3)	0.9213 (19)	0.4687 (10)	0.027 (4)*
H2A	0.175 (3)	0.868 (2)	0.3865 (11)	0.032 (5)*
C3	0.2232 (3)	0.69623 (16)	0.46223 (8)	0.0236 (3)
H3A	0.331 (3)	0.6804 (19)	0.5103 (10)	0.027 (4)*
H3B	0.049 (4)	0.6953 (19)	0.4749 (10)	0.032 (5)*
C4	0.2753 (3)	0.57716 (16)	0.40620 (8)	0.0230 (3)
H4B	0.166 (3)	0.588 (2)	0.3604 (10)	0.033 (5)*
H4A	0.245 (3)	0.4812 (19)	0.4270 (9)	0.027 (4)*
C5	0.5391 (3)	0.58557 (14)	0.38390 (8)	0.0212 (3)
H5B	0.657 (3)	0.5641 (18)	0.4283 (9)	0.021 (4)*
H5A	0.565 (3)	0.5139 (19)	0.3448 (9)	0.023 (4)*
C6	0.6852 (2)	0.76255 (14)	0.29111 (7)	0.0170 (3)
C7	0.7267 (2)	0.63574 (14)	0.23861 (7)	0.0180 (3)
H7B	0.575 (3)	0.5836 (18)	0.2286 (9)	0.022 (4)*
H7A	0.854 (3)	0.5704 (19)	0.2607 (9)	0.024 (4)*
C8	0.8154 (2)	0.69439 (14)	0.16614 (7)	0.0190 (3)
C9	1.0830 (3)	0.73141 (18)	0.16694 (9)	0.0270 (3)
H9C	1.137 (4)	0.780 (2)	0.2127 (12)	0.046 (6)*
H9B	1.177 (4)	0.639 (2)	0.1650 (12)	0.049 (6)*
H9A	1.116 (4)	0.784 (2)	0.1229 (13)	0.053 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0316 (5)	0.0149 (5)	0.0240 (5)	0.0001 (4)	0.0072 (4)	0.0018 (4)
O2	0.0346 (6)	0.0292 (6)	0.0191 (5)	−0.0014 (4)	−0.0030 (4)	0.0028 (4)
N1	0.0295 (6)	0.0133 (5)	0.0183 (5)	−0.0003 (4)	0.0048 (4)	−0.0007 (4)
C1	0.0284 (7)	0.0164 (6)	0.0183 (6)	−0.0016 (5)	0.0035 (5)	−0.0030 (5)
C2	0.0285 (7)	0.0198 (7)	0.0226 (7)	0.0029 (5)	0.0024 (5)	−0.0021 (5)
C3	0.0231 (7)	0.0237 (7)	0.0244 (7)	−0.0008 (5)	0.0040 (5)	−0.0001 (5)
C4	0.0269 (7)	0.0208 (7)	0.0209 (7)	−0.0043 (5)	−0.0007 (5)	0.0003 (5)
C5	0.0309 (7)	0.0144 (6)	0.0188 (6)	−0.0006 (5)	0.0042 (5)	0.0020 (5)
C6	0.0167 (6)	0.0164 (6)	0.0176 (6)	0.0011 (5)	−0.0006 (5)	0.0005 (5)
C7	0.0200 (6)	0.0156 (6)	0.0183 (6)	0.0004 (5)	0.0015 (5)	0.0000 (5)
C8	0.0249 (7)	0.0142 (6)	0.0183 (6)	0.0023 (5)	0.0032 (5)	−0.0013 (5)
C9	0.0238 (7)	0.0298 (8)	0.0281 (8)	0.0013 (6)	0.0076 (6)	0.0033 (6)

Geometric parameters (Å, º) top

O1—C6	1.2353 (16)	C4—C5	1.523 (2)
O2—C8	1.2117 (17)	C4—H4B	0.980 (18)
N1—C6	1.3472 (17)	C4—H4A	0.976 (18)
N1—C5	1.4667 (16)	C5—H5B	1.001 (16)
N1—C1	1.4706 (16)	C5—H5A	0.978 (17)
C1—C2	1.521 (2)	C6—C7	1.5244 (18)
C1—H1B	1.001 (16)	C7—C8	1.5171 (18)
C1—H1A	0.981 (17)	C7—H7B	0.959 (17)
C2—C3	1.525 (2)	C7—H7A	0.976 (17)
C2—H2B	0.987 (18)	C8—C9	1.496 (2)
C2—H2A	0.981 (19)	C9—H9C	0.96 (2)
C3—C4	1.525 (2)	C9—H9B	0.99 (2)
C3—H3A	1.012 (17)	C9—H9A	0.95 (2)
C3—H3B	0.993 (19)

C6—N1—C5	125.13 (11)	H4B—C4—H4A	107.2 (14)
C6—N1—C1	120.59 (11)	N1—C5—C4	110.79 (11)
C5—N1—C1	114.27 (10)	N1—C5—H5B	107.6 (9)
N1—C1—C2	110.57 (11)	C4—C5—H5B	110.1 (9)
N1—C1—H1B	107.1 (9)	N1—C5—H5A	110.0 (10)
C2—C1—H1B	108.7 (9)	C4—C5—H5A	110.2 (9)
N1—C1—H1A	108.0 (10)	H5B—C5—H5A	108.2 (13)
C2—C1—H1A	112.9 (9)	O1—C6—N1	122.69 (12)
H1B—C1—H1A	109.4 (13)	O1—C6—C7	119.67 (12)
C1—C2—C3	110.19 (11)	N1—C6—C7	117.64 (11)
C1—C2—H2B	110.2 (10)	C8—C7—C6	109.09 (10)
C3—C2—H2B	109.9 (10)	C8—C7—H7B	110.2 (10)
C1—C2—H2A	108.8 (11)	C6—C7—H7B	109.2 (10)
C3—C2—H2A	110.9 (11)	C8—C7—H7A	107.6 (10)
H2B—C2—H2A	106.8 (14)	C6—C7—H7A	110.8 (10)
C2—C3—C4	110.44 (12)	H7B—C7—H7A	109.9 (14)
C2—C3—H3A	108.1 (10)	O2—C8—C9	122.56 (13)
C4—C3—H3A	109.2 (10)	O2—C8—C7	120.78 (12)
C2—C3—H3B	109.2 (10)	C9—C8—C7	116.62 (12)
C4—C3—H3B	111.9 (10)	C8—C9—H9C	110.5 (13)
H3A—C3—H3B	107.8 (14)	C8—C9—H9B	108.1 (12)
C5—C4—C3	111.32 (11)	H9C—C9—H9B	107.5 (18)
C5—C4—H4B	107.5 (11)	C8—C9—H9A	110.6 (13)
C3—C4—H4B	110.3 (11)	H9C—C9—H9A	113.9 (18)
C5—C4—H4A	109.8 (10)	H9B—C9—H9A	105.9 (18)
C3—C4—H4A	110.6 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.96 (2)	2.459 (17)	3.378 (3)	161 (1)
C9—H9B···O1ⁱⁱ	0.99 (2)	2.601 (18)	3.466 (3)	146 (1)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.96 (2)	2.459 (17)	3.378 (3)	161 (1)
C9—H9B···O1ⁱⁱ	0.99 (2)	2.601 (18)	3.466 (3)	146 (1)

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

Acknowledgements

MS gratefully acknowledges a PhD grant from the Deutsche Bundesstiftung Umwelt.

References

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