organic compounds
3-Oxo-3-(piperidin-1-yl)propanenitrile
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
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
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536812035015/hb6912sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035015/hb6912Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035015/hb6912Isup3.cml
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.
All H atoms were positioned geometrically and refined using a riding model with C–H = 0.97 Å and Uiso(H) = 1.2 Ueq(C).
Data collection: APEX2 (Bruker, 2009); cell
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).Fig. 1. The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms. Fig. 2. The of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity. |
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 |
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 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) |
C8H12N2O | V = 838.69 (3) Å3 |
Mr = 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)° |
Bruker SMART APEXII CCD diffractometer | 1300 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1222 reflections with I > 2σ(I) |
Tmin = 0.656, Tmax = 0.783 | Rint = 0.030 |
5110 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.20 e Å−3 |
1300 reflections | Δρmin = −0.30 e Å−3 |
101 parameters |
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. |
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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.656, 0.783 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5110, 1300, 1222 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.20, −0.30 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
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. |
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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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].