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

Fun, H.-K.; Quah, C.K.; Abdel-Aziz, H.A.; Ghabbour, H.A.

doi:10.1107/S1600536812035015

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2726

doi:10.1107/S1600536812035015

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

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Hatem A. Abdel-Aziz ^b and Hazem A. Ghabbour ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: hkfun@usm.my

(Received 24 July 2012; accepted 8 August 2012; online 15 August 2012)

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, P 2₁ /c
a = 9.7106 (2) Å
b = 8.9468 (2) Å
c = 9.8487 (2) Å
β = 101.425 (1)°
V = 838.69 (3) Å³
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[F² > 2σ(F²)] = 0.053
wR(F²) = 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

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) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035015/hb6912sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035015/hb6912Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035015/hb6912Isup3.cml

checkCIF report

Comment top

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].

Related literature top

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 top

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.

Computing details top

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

Figures top

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.

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

Crystal data top

C₈H₁₂N₂O	F(000) = 328
M_r = 152.20	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0759P)² + 0.0948P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
1300 reflections	Δρ_max = 0.20 e Å⁻³
101 parameters	Δρ_min = −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)

Crystal data top

C₈H₁₂N₂O	V = 838.69 (3) Å³
M_r = 152.20	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 9.7106 (2) Å	µ = 0.66 mm⁻¹
b = 8.9468 (2) Å	T = 296 K
c = 9.8487 (2) Å	0.70 × 0.62 × 0.39 mm
β = 101.425 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1300 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1222 reflections with I > 2σ(I)
T_min = 0.656, T_max = 0.783	R_int = 0.030
5110 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.12	Δρ_max = 0.20 e Å⁻³
1300 reflections	Δρ_min = −0.30 e Å⁻³
101 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₈H₁₂N₂O
M_r	152.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.7106 (2), 8.9468 (2), 9.8487 (2)
β (°)	101.425 (1)
V (Å³)	838.69 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.70 × 0.62 × 0.39

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.656, 0.783
No. of measured, independent and observed [I > 2σ(I)] reflections	5110, 1300, 1222
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.578

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.128, 1.12
No. of reflections	1300
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.30

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

The authors thank the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University. HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160).

References

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