Crystal structure of 2,2-di­chloro-1-(piperidin-1-yl)ethanone

Schwierz, M.; Görls, H.; Imhof, W.

doi:10.1107/S205698901402708X

organic compounds

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Volume 71| Part 1| January 2015| Page o47

https://doi.org/10.1107/S205698901402708X

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Crystal structure of 2,2-dichloro-1-(piperidin-1-yl)ethanone

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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 December 2014; accepted 10 December 2014; online 1 January 2015)

In the title compound, C₇H₁₁Cl₂NO, the piperidine ring shows a chair conformation and the bond-angle sum at the N atom is 359.9°. The H atom of the dichloromethyl group is in an eclipsed conformation with respect to the carbonyl group (H—C—C=O = −5°). In the crystal, inversion dimers are linked by pairs of C—H⋯O hydrogen bonds between the dichloromethyl group and the carbonyl O atom, which generate R₂²(8) loops. The dimers are linked into a ladder-like structure propagating in the [100] direction by short O⋯Cl [3.1084 (9) Å] contacts.

Keywords: crystal structure; piperidine ring; ethanone; weak hydrogen bonds; intermolecular Cl⋯O interactions.

CCDC reference: 1038542

1. Related literature

For the synthetic procedure, see: Schank (1967 ). For a survey concerning weak hydrogen bonds, see: Desiraju & Steiner (1999 ). For a description of the nature of intermolecular interactions between chlorine and oxygen, see: Lommerse et al. (1996 ). For the crystal structure of the starting compound, see: Schwierz et al. (2015 ).

2. Experimental

2.1. Crystal data

C₇H₁₁Cl₂NO
M_r = 196.07
Monoclinic, P 2₁ /n
a = 6.2972 (1) Å
b = 15.4896 (2) Å
c = 9.3709 (2) Å
β = 108.920 (1)°
V = 864.66 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 133 K
0.08 × 0.07 × 0.06 mm

2.2. Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.712, T_max = 0.746
5528 measured reflections
1982 independent reflections
1909 reflections with I > 2σ(I)
R_int = 0.014

2.3. Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.051
S = 1.07
1982 reflections
144 parameters
All H-atom parameters refined
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.927 (13)	2.286 (12)	3.1931 (13)	166 (1)
Symmetry code: (i) -x+2, -y+1, -z+1.

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., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 1038542

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S205698901402708X/hb7336sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901402708X/hb7336Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901402708X/hb7336Isup3.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 2,2-dichloro-1-(piperidin-1-yl)butane-1,3-dione (Schwierz et al., 2015) following a modified procedure (Schank, 1967). As it is expected the piperidine ring shows a chair conformation and the amide substructure is planar. The hydrogen atom of the dichloromethyl group is in an eclipsed conformation with respect to the carbonyl group. In the crystal structure, dimeric aggregates are formed by hydrogen bonds of the C–H···O type between the dichloromethyl group and the carbonyl oxygen atom. In addition, these dimers are linked into a ladder-like structure parallel to the ac plane by oxygen chlorine contacts.

Related literature top

For the synthetic procedure, see: Schank (1967). For a survey concerning weak hydrogen bonds, see: Desiraju & Steiner (1999). For a description of the nature of intermolecular interactions between chlorine and oxygen, see: Lommerse et al. (1996). For the crystal structure of the starting compound, see: Schwierz et al. (2015).

Experimental top

22 ml methanol was cooled down to -6°C and then 1.93 g (84 mmol) sodium was slowly added in a way that the temperature is maintained. Afterwards 20.0 g (84 mmol) 2,2-dichloro-1-(piperidin-1-yl)butane-1,3-dione in 10 ml methanol was dropwise added to the solution of NaOMe. The resulting solution was stirred for 30 minutes and then neutralized with aqueous HCl at -10°C. After evaporating the mixture to dryness the amorphous material was collected on filter paper in a Büchner funnel and washed with water (yield: 13.6 g, 83%). The product has to be destilled in vacuo (0.2 mbar) and condensed into a Schlenk tube cooled by liquid nitrogen to obtain colourless prisms for X-ray diffraction.

Structure description top

For the synthetic procedure, see: Schank (1967). For a survey concerning weak hydrogen bonds, see: Desiraju & Steiner (1999). For a description of the nature of intermolecular interactions between chlorine and oxygen, see: Lommerse et al. (1996). For the crystal structure of the starting compound, see: Schwierz et al. (2015).

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., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. : Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. : Crystal structure of the title compound showing ladder-like arrangement parallel to the ac plane.

2,2-Dichloro-1-(piperidin-1-yl)ethanone top

Crystal data top

C₇H₁₁Cl₂NO	Z = 4
M_r = 196.07	F(000) = 408
Monoclinic, P2₁/n	D_x = 1.506 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.2972 (1) Å	µ = 0.69 mm⁻¹
b = 15.4896 (2) Å	T = 133 K
c = 9.3709 (2) Å	Prism, colourless
β = 108.920 (1)°	0.08 × 0.07 × 0.06 mm
V = 864.66 (3) Å³

Data collection top

Nonius KappaCCD diffractometer	1982 independent reflections
Radiation source: fine-focus sealed tube	1909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
phi– + ω–scan	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.712, T_max = 0.746	k = −17→20
5528 measured reflections	l = −12→8

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)] = 0.020	Hydrogen site location: difference Fourier map
wR(F²) = 0.051	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0187P)² + 0.3796P] where P = (F_o² + 2F_c²)/3
1982 reflections	(Δ/σ)_max = 0.001
144 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₇H₁₁Cl₂NO	V = 864.66 (3) Å³
M_r = 196.07	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2972 (1) Å	µ = 0.69 mm⁻¹
b = 15.4896 (2) Å	T = 133 K
c = 9.3709 (2) Å	0.08 × 0.07 × 0.06 mm
β = 108.920 (1)°

Data collection top

Nonius KappaCCD diffractometer	1982 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1909 reflections with I > 2σ(I)
T_min = 0.712, T_max = 0.746	R_int = 0.014
5528 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.051	All H-atom parameters refined
S = 1.07	Δρ_max = 0.36 e Å⁻³
1982 reflections	Δρ_min = −0.18 e Å⁻³
144 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
Cl1	0.58896 (4)	0.397515 (17)	0.60904 (3)	0.01933 (8)
Cl2	1.00866 (4)	0.453542 (17)	0.83711 (3)	0.01976 (8)
O1	1.06874 (14)	0.38479 (5)	0.48067 (9)	0.02086 (18)
N1	1.05601 (15)	0.28336 (6)	0.65192 (10)	0.01611 (18)
C1	1.20371 (19)	0.22440 (7)	0.60412 (13)	0.0191 (2)
H1B	1.333 (2)	0.2132 (9)	0.6929 (16)	0.023 (3)*
H1A	1.254 (2)	0.2541 (9)	0.5296 (16)	0.021 (3)*
C2	1.0825 (2)	0.14060 (7)	0.54290 (13)	0.0187 (2)
H2B	0.959 (2)	0.1519 (9)	0.4527 (17)	0.023 (3)*
H2A	1.189 (2)	0.1027 (9)	0.5171 (17)	0.026 (4)*
C3	0.99241 (19)	0.09891 (7)	0.65911 (13)	0.0185 (2)
H3B	0.910 (2)	0.0471 (9)	0.6184 (15)	0.019 (3)*
H3A	1.119 (2)	0.0834 (9)	0.7476 (16)	0.022 (3)*
C4	0.84334 (18)	0.16225 (7)	0.70759 (12)	0.0170 (2)
H4B	0.713 (2)	0.1755 (9)	0.6231 (15)	0.019 (3)*
H4A	0.792 (2)	0.1379 (9)	0.7849 (16)	0.022 (3)*
C5	0.96872 (19)	0.24606 (7)	0.76638 (12)	0.0167 (2)
H5B	1.098 (2)	0.2349 (9)	0.8562 (15)	0.018 (3)*
H5A	0.875 (2)	0.2867 (9)	0.7911 (15)	0.018 (3)*
C6	1.00703 (17)	0.36088 (7)	0.58641 (11)	0.0140 (2)
C7	0.87376 (17)	0.42766 (7)	0.64343 (11)	0.0141 (2)
H7	0.874 (2)	0.4785 (8)	0.5911 (14)	0.013 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01372 (13)	0.02241 (14)	0.02175 (14)	−0.00113 (10)	0.00559 (10)	−0.00364 (10)
Cl2	0.02030 (14)	0.01973 (14)	0.01757 (13)	−0.00162 (10)	0.00382 (10)	−0.00656 (9)
O1	0.0272 (4)	0.0187 (4)	0.0225 (4)	0.0016 (3)	0.0162 (3)	0.0043 (3)
N1	0.0203 (4)	0.0119 (4)	0.0204 (4)	0.0008 (3)	0.0126 (4)	0.0009 (3)
C1	0.0189 (5)	0.0149 (5)	0.0278 (6)	0.0014 (4)	0.0136 (5)	0.0003 (4)
C2	0.0213 (5)	0.0154 (5)	0.0218 (5)	0.0021 (4)	0.0103 (4)	−0.0008 (4)
C3	0.0214 (5)	0.0125 (5)	0.0214 (5)	−0.0016 (4)	0.0065 (4)	0.0003 (4)
C4	0.0181 (5)	0.0167 (5)	0.0173 (5)	−0.0017 (4)	0.0071 (4)	0.0027 (4)
C5	0.0226 (5)	0.0142 (5)	0.0160 (5)	0.0003 (4)	0.0101 (4)	0.0020 (4)
C6	0.0137 (5)	0.0138 (5)	0.0152 (5)	−0.0025 (4)	0.0054 (4)	−0.0012 (4)
C7	0.0150 (5)	0.0136 (5)	0.0146 (5)	−0.0014 (4)	0.0057 (4)	−0.0004 (4)

Geometric parameters (Å, º) top

Cl1—C7	1.7786 (10)	C2—H2A	0.977 (15)
Cl2—C7	1.7823 (10)	C3—C4	1.5254 (15)
O1—C6	1.2328 (13)	C3—H3B	0.966 (14)
N1—C6	1.3383 (14)	C3—H3A	0.974 (15)
N1—C5	1.4726 (13)	C4—C5	1.5264 (15)
N1—C1	1.4731 (13)	C4—H4B	0.961 (14)
C1—C2	1.5208 (15)	C4—H4A	0.961 (14)
C1—H1B	0.973 (15)	C5—H5B	0.980 (14)
C1—H1A	0.971 (14)	C5—H5A	0.942 (14)
C2—C3	1.5249 (15)	C6—C7	1.5332 (14)
C2—H2B	0.960 (15)	C7—H7	0.927 (13)

C6—N1—C5	126.95 (9)	C3—C4—C5	110.99 (9)
C6—N1—C1	119.41 (9)	C3—C4—H4B	109.7 (8)
C5—N1—C1	113.57 (8)	C5—C4—H4B	108.7 (8)
N1—C1—C2	110.77 (9)	C3—C4—H4A	111.2 (8)
N1—C1—H1B	106.7 (8)	C5—C4—H4A	108.9 (8)
C2—C1—H1B	110.4 (8)	H4B—C4—H4A	107.2 (11)
N1—C1—H1A	108.1 (8)	N1—C5—C4	110.02 (9)
C2—C1—H1A	112.0 (8)	N1—C5—H5B	106.9 (8)
H1B—C1—H1A	108.8 (12)	C4—C5—H5B	110.5 (8)
C1—C2—C3	110.46 (9)	N1—C5—H5A	109.2 (8)
C1—C2—H2B	109.9 (9)	C4—C5—H5A	111.4 (8)
C3—C2—H2B	109.0 (8)	H5B—C5—H5A	108.8 (11)
C1—C2—H2A	107.8 (8)	O1—C6—N1	123.54 (10)
C3—C2—H2A	111.4 (8)	O1—C6—C7	115.35 (9)
H2B—C2—H2A	108.3 (12)	N1—C6—C7	121.09 (9)
C2—C3—C4	110.35 (9)	C6—C7—Cl1	113.17 (7)
C2—C3—H3B	110.4 (8)	C6—C7—Cl2	111.88 (7)
C4—C3—H3B	110.3 (8)	Cl1—C7—Cl2	111.30 (5)
C2—C3—H3A	108.8 (8)	C6—C7—H7	107.1 (8)
C4—C3—H3A	108.4 (8)	Cl1—C7—H7	107.6 (8)
H3B—C3—H3A	108.6 (11)	Cl2—C7—H7	105.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.927 (13)	2.286 (12)	3.1931 (13)	166 (1)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.927 (13)	2.286 (12)	3.1931 (13)	166 (1)

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

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

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