3-Oxo-3-(piperidin-1-yl)propane­nitrile

Abstract

In the title compound, C₈H₁₂N₂O, the piperidine ring exhibits a chair conformation and its least-squares plane (all atoms) makes a dihedral angle of 32.88 (12)° with the propane­nitrile unit (r.m.s. deviation = 0.001 Å). In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming chains along [001].

Related literature  

For ring conformations, see: Cremer & Pople (1975 ▶). For background to piperidine derivatives, see: Andrews et al. (2008 ▶); Abdel-Aziz & Mekawey (2009 ▶); Abdel-Aziz et al. (2009 ▶, 2011 ▶). For the synthesis, see: Whitehead & Traverso (1955 ▶).

Experimental  

Crystal data  

• C₈H₁₂N₂O

• M _r = 152.20

• Monoclinic,

• a = 9.7106 (2) Å

• b = 8.9468 (2) Å

• c = 9.8487 (2) Å

• β = 101.425 (1)°

• V = 838.69 (3) ų

• Z = 4

• Cu Kα radiation

• μ = 0.66 mm⁻¹

• T = 296 K

• 0.70 × 0.62 × 0.39 mm

Data collection  

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.656, T _max = 0.783

• 5110 measured reflections

• 1300 independent reflections

• 1222 reflections with I > 2σ(I)

• R _int = 0.030

Refinement  

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 0.128

• S = 1.12

• 1300 reflections

• 101 parameters

• H-atom parameters constrained

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812035015/hb6912Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O1i	0.97	2.23	3.1922 (17)	170

Symmetry code: (i) .

supplementary crystallographic information

Comment

Piperidines are an important class of heterocycles found in numerous natural products and medicinal structures (Andrews et al., 2008). In continuation of our interest in the chemistry of piperidines (Abdel-Aziz & Mekawey, 2009; Abdel-Aziz et al., 2009, 2011), we report here the crystal structure of the title compound.

In the title molecule, Fig. 1, the piperidin-1-yl ring (N1/C1-C5) exhibits a chair conformation, puckering parameters (Cremer & Pople, 1975) Q = 0.5455 (18) Å; Θ = 1.84 (19)° and φ = 113 (6)Å, and its least square plane makes a dihedral angle of 32.88 (12)° with the propanenitrile unit (N2/C6-C8, r.m.s. deviation = 0.001 Å).

In the crystal (Fig.2), molecules are linked via C7–H7A···O1 hydrogen bonds (Table 1), forming chains along [001].

Experimental

The title compound was prepared by the reaction of ethyl cyanoacetate with piperidine according to the reported method (Whitehead et al., 1955). Colourless blocks were obtained by slowly evaporating an ethanol solution at room temperature.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C–H = 0.97 Å and U_iso(H) = 1.2 U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms.

Fig. 2.

The crystal structure of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

Crystal data

C8H12N2O	F(000) = 328
Mr = 152.20	Dx = 1.205 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 2826 reflections
a = 9.7106 (2) Å	θ = 4.6–70.9°
b = 8.9468 (2) Å	µ = 0.66 mm−1
c = 9.8487 (2) Å	T = 296 K
β = 101.425 (1)°	Block, colourless
V = 838.69 (3) Å3	0.70 × 0.62 × 0.39 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	1300 independent reflections
Radiation source: fine-focus sealed tube	1222 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 63.0°, θmin = 4.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.656, Tmax = 0.783	k = −7→10
5110 measured reflections	l = −11→11

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053	H-atom parameters constrained
wR(F2) = 0.128	w = 1/[σ2(Fo2) + (0.0759P)2 + 0.0948P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max = 0.001
1300 reflections	Δρmax = 0.20 e Å−3
101 parameters	Δρmin = −0.30 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.82 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.24331 (12)	0.06319 (12)	0.22467 (11)	0.0473 (4)
N2	0.08305 (19)	0.56540 (17)	0.19855 (19)	0.0850 (6)
O1	0.24717 (12)	0.26280 (12)	0.36568 (9)	0.0599 (5)
C1	0.19317 (15)	−0.01701 (16)	0.09524 (15)	0.0514 (5)
H1A	0.1452	0.0519	0.0257	0.062*
H1B	0.1266	−0.0934	0.1097	0.062*
C2	0.31440 (19)	−0.08861 (19)	0.04488 (17)	0.0637 (5)
H2A	0.3752	−0.0113	0.0205	0.076*
H2B	0.2787	−0.1468	−0.0377	0.076*
C3	0.39850 (19)	−0.1892 (2)	0.15449 (19)	0.0683 (6)
H3A	0.3414	−0.2738	0.1705	0.082*
H3B	0.4801	−0.2269	0.1224	0.082*
C4	0.44535 (18)	−0.10440 (19)	0.28805 (19)	0.0673 (6)
H4A	0.4908	−0.1729	0.3594	0.081*
H4B	0.5136	−0.0293	0.2751	0.081*
C5	0.32379 (19)	−0.0296 (2)	0.33513 (16)	0.0635 (5)
H5A	0.2627	−0.1051	0.3621	0.076*
H5B	0.3590	0.0322	0.4155	0.076*
C6	0.20841 (13)	0.20271 (15)	0.25256 (12)	0.0425 (5)
C7	0.11643 (16)	0.28844 (15)	0.13497 (14)	0.0491 (5)
H7A	0.1588	0.2852	0.0537	0.059*
H7B	0.0250	0.2410	0.1116	0.059*
C8	0.09924 (16)	0.44374 (17)	0.17336 (16)	0.0558 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0568 (7)	0.0441 (7)	0.0387 (7)	0.0043 (5)	0.0038 (5)	0.0000 (4)
N2	0.0915 (12)	0.0557 (10)	0.1066 (14)	0.0150 (8)	0.0165 (9)	−0.0146 (8)
O1	0.0771 (8)	0.0609 (8)	0.0407 (7)	−0.0035 (5)	0.0090 (5)	−0.0114 (4)
C1	0.0560 (8)	0.0436 (8)	0.0495 (8)	0.0026 (6)	−0.0017 (6)	−0.0064 (6)
C2	0.0770 (11)	0.0552 (10)	0.0575 (9)	0.0141 (7)	0.0097 (8)	−0.0108 (7)
C3	0.0657 (10)	0.0527 (10)	0.0837 (13)	0.0142 (7)	0.0077 (8)	−0.0032 (8)
C4	0.0628 (10)	0.0564 (10)	0.0736 (11)	0.0085 (7)	−0.0083 (8)	0.0097 (7)
C5	0.0808 (11)	0.0605 (10)	0.0448 (9)	0.0074 (7)	0.0018 (7)	0.0103 (6)
C6	0.0476 (7)	0.0455 (8)	0.0364 (7)	−0.0053 (5)	0.0133 (5)	−0.0027 (5)
C7	0.0615 (9)	0.0436 (9)	0.0428 (8)	0.0051 (6)	0.0115 (6)	−0.0030 (5)
C8	0.0597 (9)	0.0496 (10)	0.0600 (9)	0.0057 (6)	0.0167 (7)	−0.0037 (6)

Geometric parameters (Å, º)

N1—C6	1.3361 (18)	C3—H3A	0.9700
N1—C1	1.4597 (16)	C3—H3B	0.9700
N1—C5	1.4650 (17)	C4—C5	1.508 (3)
N2—C8	1.134 (2)	C4—H4A	0.9700
O1—C6	1.2271 (16)	C4—H4B	0.9700
C1—C2	1.508 (2)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—C7	1.5224 (18)
C2—C3	1.514 (2)	C7—C8	1.458 (2)
C2—H2A	0.9700	C7—H7A	0.9700
C2—H2B	0.9700	C7—H7B	0.9700
C3—C4	1.508 (2)
C6—N1—C1	125.76 (11)	C5—C4—H4A	109.2
C6—N1—C5	119.75 (11)	C3—C4—H4A	109.2
C1—N1—C5	113.99 (12)	C5—C4—H4B	109.2
N1—C1—C2	110.43 (11)	C3—C4—H4B	109.2
N1—C1—H1A	109.6	H4A—C4—H4B	107.9
C2—C1—H1A	109.6	N1—C5—C4	110.98 (13)
N1—C1—H1B	109.6	N1—C5—H5A	109.4
C2—C1—H1B	109.6	C4—C5—H5A	109.4
H1A—C1—H1B	108.1	N1—C5—H5B	109.4
C1—C2—C3	111.34 (14)	C4—C5—H5B	109.4
C1—C2—H2A	109.4	H5A—C5—H5B	108.0
C3—C2—H2A	109.4	O1—C6—N1	123.45 (12)
C1—C2—H2B	109.4	O1—C6—C7	119.88 (12)
C3—C2—H2B	109.4	N1—C6—C7	116.67 (11)
H2A—C2—H2B	108.0	C8—C7—C6	111.28 (11)
C4—C3—C2	110.49 (13)	C8—C7—H7A	109.4
C4—C3—H3A	109.6	C6—C7—H7A	109.4
C2—C3—H3A	109.6	C8—C7—H7B	109.4
C4—C3—H3B	109.6	C6—C7—H7B	109.4
C2—C3—H3B	109.6	H7A—C7—H7B	108.0
H3A—C3—H3B	108.1	N2—C8—C7	177.51 (18)
C5—C4—C3	111.85 (14)
C6—N1—C1—C2	131.80 (14)	C3—C4—C5—N1	−53.1 (2)
C5—N1—C1—C2	−56.33 (17)	C1—N1—C6—O1	175.87 (13)
N1—C1—C2—C3	55.29 (18)	C5—N1—C6—O1	4.4 (2)
C1—C2—C3—C4	−54.4 (2)	C1—N1—C6—C7	−4.54 (19)
C2—C3—C4—C5	53.3 (2)	C5—N1—C6—C7	−175.99 (12)
C6—N1—C5—C4	−132.36 (14)	O1—C6—C7—C8	6.13 (18)
C1—N1—C5—C4	55.23 (18)	N1—C6—C7—C8	−173.48 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O1i	0.97	2.23	3.1922 (17)	170

Symmetry code: (i) x, −y+1/2, z−1/2.