organic papers
o98
Lemmereret al. C14H17NO doi:10.1107/S160053680605152X Acta Cryst.(2007). E63, o98–o99 Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
(2
E
)-2-(1-Methylpiperidin-2-ylidene)-1-phenyl-ethanone
Andreas Lemmerer, Joseph P. Michael,* Daniel P. Pienaar and Desigan Sannasy
Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO Wits 2050, South Africa
Correspondence e-mail: jmichael@chem.wits.ac.za
Key indicators
Single-crystal X-ray study
T= 173 K
Mean(C–C) = 0.003 A˚ Disorder in main residue
Rfactor = 0.051
wRfactor = 0.199
Data-to-parameter ratio = 13.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 2 November 2006 Accepted 28 November 2006
#2007 International Union of Crystallography
All rights reserved
In the title compound, C14H17NO, the piperidine ring is in a
half-chair conformation. The molecules are linked into C(7) chains by an intermolecular C—H O hydrogen bond.
Comment
Enaminones (-acylated enamines) feature prominently in our research programme as intermediates for the synthesis of alkaloids and other nitrogen-containing heterocycles (Michael
et al., 1999). We required the title compound, (I), a simple enaminone, as a model for probing the reactivity of exocyclic enaminones towards reducing agents. Compound (I) has previously been prepared as a key intermediate in the synth-esis of piperidine alkaloids isolated from the genus Sedum
(Ghiaci & Adibi, 1996).
A view of the molecular structure of (I) is given in Fig. 1. The piperidine ring adopts a half-chair conformation [puck-ering amplitude QT = 0.551 (4) A˚ , = 124.0(3 and ’ =
22.8 (4) (Cremer & Pople, 1975)]. The bond lengths for the enaminone functionality from N1 to O1 are comparable with values reported in the literature (Allen et al., 1987), but the delocalization does not extend to the phenyl ring [O1—C9— C10—C11 =15.8 (3)].
The crystal structure of (I) is built up by an intramolecular C—H O hydrogen bond and weak intermolecular C— H O hydrogen bonds that link the molecules into chains. Atom C7 in the molecule at (x,y,z) acts as a hydrogen-bond donorviaatom H7Ato atom O1 in the molecule at (x,1
2y, z1
2), thereby generating by translation aC(7) chain (Etteret al., 1990; Bernsteinet al., 1995) running parallel to the [001] direction (Fig. 2 and Table 1).
Experimental
(2E)-2-(1-Methylpiperidin-2-ylidene)-1-phenylethanone, (I), was prepared in 77% yield from 1-methylpiperidine-2-thione and phenacyl bromide by the method of Ghiaci & Adibi (1996) (m.p. 340– 343 K; literature m.p. 341–343 K). 1H NMR (300 MHz, CDCl
3): 7.83–7.86 (2H,m, 11-H and 15-H), 7.35–7.39 (3H,m, 12-H, 13-H, 14-H), 5.65 (1H, s, 8-H), 3.31–3.45 (4H,m, 3-H and 6-H), 2.98 (3H,s, NCH3), 1.78–1.86 and 1.65–1.71 (4H, 2m, 4-H and 5-H);
(C13), 127.9 and 127.1 (C11, C12, C14, C15), 90.7 (C8), 52.0 (C6), 40.2 (NCH3), 28.3 (C3), 23.1 and 19.4 (C4, C5). Crystals suitable for X-ray crystallography were obtained as pale-brown blocks by slow growth from a solution in EtOAc/hexane (approximately 1:1).
Crystal data
C14H17NO Mr= 215.29 Monoclinic,P21=c a= 8.006 (2) A˚ b= 9.441 (3) A˚ c= 15.535 (4) A˚ = 95.197 (6) V= 1169.5 (6) A˚3
Z= 4
Dx= 1.223 Mg m3 MoKradiation = 0.08 mm1 T= 173 (2) K Block, pale brown 0.380.280.24 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.962,Tmax= 0.982
5068 measured reflections 2178 independent reflections 1563 reflections withI> 2(I) Rint= 0.037
max= 25.5
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.051 wR(F2) = 0.199 S= 1.06 2178 reflections 164 parameters
H-atom parameters constrained w= 1/[2(F
o2) + (0.1371P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.24 e A˚3
min=0.34 e A˚3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C3—H3D O1 0.99 2.21 2.804 (3) 117
C7—H7A O1i
0.98 2.54 3.469 (3) 159
Symmetry code: (i)x;yþ1 2;z
1 2.
Atoms C4 and C5 of the piperidine ring (see Fig. 1) are disordered. They were resolved by finding alternative positions from the differ-ence Fourier map, and subsequently refined anisotropically over two positions with an occupancy of 0.607 (6) for C4A and C5A, and 0.393 (6) for the alternative positions C4Band C5B. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H bond lengths of 0.95 (aromatic CH), 0.98 (CH3), 0.99 (CH2) or 0.95 A˚ (CH), and isotropic displacement parameters equal to 1.2 (CH and CH2) or 1.5 (CH3) timesUeqof the parent atom.
Data collection:SMART(Bruker, 1998); cell refinement:SMART; data reduction: SAINT-Plus (Bruker (1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:
ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Bran-denburg, 1999); software used to prepare material for publication:
WinGX(Farrugia, 1999) andPLATON(Spek, 2003).
This work was supported by grants from the National Research Foundation, Pretoria (NRF, GUN 2053652) and the University of the Witwatersrand.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555–1573.
Brandenburg, K. (1999). DIAMOND. Version 2.1e. Crystal Impact GbR, Bonn, Germany.
Bruker (1998). SMART-NT. Version 5.050. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1999).SAINT-Plus. Version 6.02 (includingXPREP). Bruker AXS Inc., Madison, Wisconsin, USA.
Cremer, D. & Pople, J. A. (1975).J. Am. Chem. Soc.97, 1354–1358. Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990).Acta Cryst.B46, 256–262. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.
Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.
Ghiaci, M. & Adibi, M. (1996).Org. Prep. Proc. Int.28, 474–477.
Michael, J. P., de Koning, C. B., Gravestock, D., Hosken, G. D., Howard, A. S., Jungmann, C. M., Krause, R. W. M., Parsons, A. S., Pelly, S. C. & Stanbury, T. V. (1999).Pure Appl. Chem.71, 979–988.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Go¨ttingen, Germany.
[image:2.610.337.537.73.217.2]Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.
Figure 1
[image:2.610.316.563.281.419.2]The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Atoms C4 and C5 in the piperidine ring are disordered; the minor occupancy disordered component is shown with dashed bonds.
Figure 2
supporting information
sup-1 Acta Cryst. (2007). E63, o98–o99
supporting information
Acta Cryst. (2007). E63, o98–o99 [https://doi.org/10.1107/S160053680605152X]
(2
E
)-2-(1-Methylpiperidin-2-ylidene)-1-phenylethanone
Andreas Lemmerer, Joseph P. Michael, Daniel P. Pienaar and Desigan Sannasy
(2E)-2-(1-Methylpiperidin-2-ylidene)-1-phenylethanone
Crystal data
C14H17NO
Mr = 215.29
Monoclinic, P21/c Hall symbol: -P 2ybc a = 8.006 (2) Å b = 9.441 (3) Å c = 15.535 (4) Å β = 95.197 (6)° V = 1169.5 (6) Å3
Z = 4
F(000) = 464 Dx = 1.223 Mg m−3
Melting point = 340–343 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 979 reflections θ = 2.6–27.7°
µ = 0.08 mm−1
T = 173 K Block, pale brown 0.38 × 0.28 × 0.24 mm
Data collection
Bruker SMART CCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.962, Tmax = 0.982 5068 measured reflections
2178 independent reflections 1563 reflections with I > 2σ(I) Rint = 0.037
θmax = 25.5°, θmin = 2.5°
h = −9→9 k = −9→11 l = −18→14
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.051
wR(F2) = 0.199
S = 1.06 2178 reflections 164 parameters
205 restraints
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.1371P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
Δρmax = 0.24 e Å−3 Δρmin = −0.34 e Å−3
Special details
Experimental. absorption corrections were made using the program SADABS (Sheldrick, 1996).
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq Occ. (<1)
C2 0.4632 (2) 0.2460 (2) 0.49237 (12) 0.0264 (5)
C3 0.3064 (3) 0.2206 (3) 0.53690 (13) 0.0355 (5)
H3A 0.2715 0.3107 0.5625 0.043* 0.607 (6)
H3B 0.3318 0.1523 0.5846 0.043* 0.607 (6)
H3C 0.229 0.3014 0.5248 0.043* 0.393 (6)
H3D 0.3364 0.2173 0.6001 0.043* 0.393 (6)
C4A 0.1590 (4) 0.1624 (4) 0.4753 (2) 0.0338 (10) 0.607 (6)
H4A1 0.0643 0.1356 0.5087 0.041* 0.607 (6)
H4A2 0.1194 0.236 0.4328 0.041* 0.607 (6)
C5A 0.2206 (6) 0.0339 (5) 0.4288 (3) 0.0378 (11) 0.607 (6)
H5A1 0.1266 −0.0111 0.393 0.045* 0.607 (6)
H5A2 0.2692 −0.0366 0.4711 0.045* 0.607 (6)
C4B 0.2162 (8) 0.0849 (7) 0.5090 (3) 0.0420 (18) 0.393 (6)
H4B1 0.1093 0.0765 0.536 0.05* 0.393 (6)
H4B2 0.2868 0.0013 0.5254 0.05* 0.393 (6)
C5B 0.1842 (7) 0.0962 (10) 0.4113 (4) 0.0401 (18) 0.393 (6)
H5B1 0.1298 0.1879 0.3954 0.048* 0.393 (6)
H5B2 0.1088 0.019 0.3889 0.048* 0.393 (6)
C6 0.3532 (3) 0.0854 (3) 0.37209 (14) 0.0366 (6)
H6A 0.4163 0.0025 0.3533 0.044* 0.607 (6)
H6B 0.2962 0.1298 0.3196 0.044* 0.607 (6)
H6C 0.3984 −0.0117 0.3802 0.044* 0.393 (6)
H6D 0.3368 0.1048 0.3093 0.044* 0.393 (6)
C7 0.6145 (3) 0.2210 (3) 0.36359 (14) 0.0369 (6)
H7A 0.6017 0.1699 0.3085 0.055*
H7B 0.7196 0.1924 0.3962 0.055*
H7C 0.6169 0.3232 0.3525 0.055*
C8 0.5942 (2) 0.3273 (2) 0.53132 (13) 0.0288 (5)
H8 0.6911 0.3377 0.5008 0.035*
C9 0.5953 (2) 0.3961 (2) 0.61296 (12) 0.0279 (5)
C10 0.7548 (2) 0.4703 (2) 0.64782 (12) 0.0267 (5)
C11 0.7452 (3) 0.5667 (2) 0.71523 (12) 0.0326 (5)
H11 0.6399 0.5847 0.7367 0.039*
C12 0.8861 (3) 0.6365 (3) 0.75130 (13) 0.0365 (5)
H12 0.8767 0.7027 0.7966 0.044*
C13 1.0406 (3) 0.6102 (2) 0.72174 (13) 0.0357 (5)
H13 1.1376 0.6581 0.7467 0.043*
C14 1.0535 (3) 0.5139 (2) 0.65557 (15) 0.0382 (6)
H14 1.1598 0.495 0.6354 0.046*
C15 0.9121 (2) 0.4451 (2) 0.61866 (14) 0.0336 (5)
H15 0.9222 0.3799 0.5729 0.04*
N1 0.4733 (2) 0.18768 (19) 0.41371 (11) 0.0311 (5)
supporting information
sup-3 Acta Cryst. (2007). E63, o98–o99
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C2 0.0262 (10) 0.0293 (11) 0.0245 (10) 0.0030 (8) 0.0069 (8) 0.0023 (8)
C3 0.0286 (11) 0.0471 (13) 0.0322 (11) −0.0085 (9) 0.0112 (9) −0.0064 (9)
C4A 0.0268 (17) 0.041 (2) 0.034 (2) −0.0064 (16) 0.0062 (15) −0.0007 (17)
C5A 0.044 (2) 0.035 (3) 0.036 (2) −0.0089 (19) 0.0073 (18) −0.0006 (18)
C4B 0.042 (3) 0.052 (4) 0.033 (3) −0.019 (3) 0.009 (2) 0.001 (3)
C5B 0.035 (3) 0.049 (5) 0.037 (3) −0.020 (3) 0.005 (3) −0.002 (3)
C6 0.0361 (12) 0.0426 (13) 0.0318 (11) −0.0089 (9) 0.0065 (9) −0.0068 (9)
C7 0.0312 (11) 0.0520 (14) 0.0293 (11) −0.0066 (10) 0.0121 (9) −0.0081 (10)
C8 0.0233 (10) 0.0362 (12) 0.0279 (10) −0.0012 (8) 0.0082 (8) 0.0003 (8)
C9 0.0233 (10) 0.0341 (12) 0.0270 (10) 0.0024 (8) 0.0065 (8) 0.0046 (8)
C10 0.0294 (10) 0.0285 (11) 0.0225 (10) 0.0024 (8) 0.0035 (8) 0.0055 (8)
C11 0.0334 (11) 0.0404 (12) 0.0249 (10) −0.0004 (9) 0.0081 (8) 0.0015 (8)
C12 0.0415 (12) 0.0437 (13) 0.0248 (11) −0.0053 (10) 0.0052 (9) −0.0033 (9) C13 0.0333 (11) 0.0400 (13) 0.0330 (12) −0.0078 (10) −0.0016 (9) 0.0037 (9)
C14 0.0300 (11) 0.0413 (13) 0.0441 (13) 0.0003 (9) 0.0075 (9) −0.0003 (10)
C15 0.0302 (11) 0.0338 (12) 0.0373 (12) 0.0012 (8) 0.0053 (9) −0.0040 (9)
N1 0.0296 (9) 0.0394 (11) 0.0252 (9) −0.0043 (7) 0.0081 (7) −0.0033 (7)
O1 0.0312 (8) 0.0633 (12) 0.0304 (8) −0.0060 (7) 0.0096 (6) −0.0112 (7)
Geometric parameters (Å, º)
C2—N1 1.350 (3) C6—H6B 0.99
C2—C8 1.393 (3) C6—H6C 0.99
C2—C3 1.506 (3) C6—H6D 0.99
C3—C4B 1.515 (5) C7—N1 1.464 (2)
C3—C4A 1.551 (4) C7—H7A 0.98
C3—H3A 0.99 C7—H7B 0.98
C3—H3B 0.99 C7—H7C 0.98
C3—H3C 0.99 C8—C9 1.424 (3)
C3—H3D 0.99 C8—H8 0.95
C4A—C5A 1.518 (5) C9—O1 1.255 (2)
C4A—H4A1 0.99 C9—C10 1.513 (3)
C4A—H4A2 0.99 C10—C11 1.395 (3)
C5A—C6 1.520 (4) C10—C15 1.397 (3)
C5A—H5A1 0.99 C11—C12 1.380 (3)
C5A—H5A2 0.99 C11—H11 0.95
C4B—C5B 1.520 (6) C12—C13 1.380 (3)
C4B—H4B1 0.99 C12—H12 0.95
C4B—H4B2 0.99 C13—C14 1.383 (3)
C5B—C6 1.537 (5) C13—H13 0.95
C5B—H5B1 0.99 C14—C15 1.384 (3)
C5B—H5B2 0.99 C14—H14 0.95
C6—N1 1.470 (3) C15—H15 0.95
N1—C2—C8 120.91 (18) C5A—C6—H6A 108.6
N1—C2—C3 118.14 (17) N1—C6—H6B 108.6
C8—C2—C3 120.96 (17) C5A—C6—H6B 108.6
C2—C3—C4B 113.5 (3) H6A—C6—H6B 107.6
C2—C3—C4A 113.09 (19) N1—C6—H6C 109.6
C2—C3—H3A 109 C5B—C6—H6C 109.6
C4A—C3—H3A 109 N1—C6—H6D 109.6
C2—C3—H3B 109 C5B—C6—H6D 109.6
C4A—C3—H3B 109 H6C—C6—H6D 108.1
H3A—C3—H3B 107.8 N1—C7—H7A 109.5
C2—C3—H3C 108.9 N1—C7—H7B 109.5
C4B—C3—H3C 108.9 H7A—C7—H7B 109.5
C2—C3—H3D 108.9 N1—C7—H7C 109.5
C4B—C3—H3D 108.9 H7A—C7—H7C 109.5
H3C—C3—H3D 107.7 H7B—C7—H7C 109.5
C5A—C4A—C3 108.3 (3) C2—C8—C9 125.59 (18)
C5A—C4A—H4A1 110 C2—C8—H8 117.2
C3—C4A—H4A1 110 C9—C8—H8 117.2
C5A—C4A—H4A2 110 O1—C9—C8 125.65 (18)
C3—C4A—H4A2 110 O1—C9—C10 116.50 (17)
H4A1—C4A—H4A2 108.4 C8—C9—C10 117.85 (17)
C4A—C5A—C6 107.1 (3) C11—C10—C15 117.83 (19)
C4A—C5A—H5A1 110.3 C11—C10—C9 117.98 (18)
C6—C5A—H5A1 110.3 C15—C10—C9 124.16 (18)
C4A—C5A—H5A2 110.3 C12—C11—C10 121.2 (2)
C6—C5A—H5A2 110.3 C12—C11—H11 119.4
H5A1—C5A—H5A2 108.5 C10—C11—H11 119.4
C3—C4B—C5B 105.0 (5) C13—C12—C11 120.2 (2)
C3—C4B—H4B1 110.7 C13—C12—H12 119.9
C5B—C4B—H4B1 110.7 C11—C12—H12 119.9
C3—C4B—H4B2 110.7 C12—C13—C14 119.6 (2)
C5B—C4B—H4B2 110.7 C12—C13—H13 120.2
H4B1—C4B—H4B2 108.8 C14—C13—H13 120.2
C4B—C5B—C6 108.4 (5) C13—C14—C15 120.2 (2)
C4B—C5B—H5B1 110 C13—C14—H14 119.9
C6—C5B—H5B1 110 C15—C14—H14 119.9
C4B—C5B—H5B2 110 C14—C15—C10 120.9 (2)
C6—C5B—H5B2 110 C14—C15—H15 119.5
H5B1—C5B—H5B2 108.4 C10—C15—H15 119.5
N1—C6—C5A 114.7 (2) C2—N1—C7 120.42 (17)
N1—C6—C5B 110.3 (3) C2—N1—C6 125.16 (17)
N1—C6—H6A 108.6 C7—N1—C6 114.39 (16)
N1—C2—C3—C4B 26.1 (4) C8—C9—C10—C11 164.01 (19)
C8—C2—C3—C4B −153.8 (4) O1—C9—C10—C15 162.0 (2)
N1—C2—C3—C4A −15.0 (3) C8—C9—C10—C15 −18.1 (3)
C8—C2—C3—C4A 165.1 (2) C15—C10—C11—C12 0.8 (3)
supporting information
sup-5 Acta Cryst. (2007). E63, o98–o99
C4B—C3—C4A—C5A −46.8 (4) C10—C11—C12—C13 −0.9 (3)
C3—C4A—C5A—C6 −65.2 (4) C11—C12—C13—C14 0.2 (3)
C2—C3—C4B—C5B −55.6 (6) C12—C13—C14—C15 0.6 (3)
C4A—C3—C4B—C5B 42.2 (4) C13—C14—C15—C10 −0.6 (3)
C3—C4B—C5B—C6 69.1 (7) C11—C10—C15—C14 −0.1 (3)
C4A—C5A—C6—N1 43.5 (4) C9—C10—C15—C14 −177.94 (19)
C4A—C5A—C6—C5B −42.5 (6) C8—C2—N1—C7 −6.6 (3)
C4B—C5B—C6—N1 −52.1 (7) C3—C2—N1—C7 173.54 (18)
C4B—C5B—C6—C5A 53.0 (6) C8—C2—N1—C6 171.43 (19)
N1—C2—C8—C9 178.57 (19) C3—C2—N1—C6 −8.5 (3)
C3—C2—C8—C9 −1.5 (3) C5A—C6—N1—C2 −6.6 (4)
C2—C8—C9—O1 −4.9 (3) C5B—C6—N1—C2 21.7 (4)
C2—C8—C9—C10 175.31 (19) C5A—C6—N1—C7 171.5 (3)
O1—C9—C10—C11 −15.8 (3) C5B—C6—N1—C7 −160.2 (3)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C3—H3D···O1 0.99 2.21 2.804 (3) 117
C7—H7A···O1i 0.98 2.54 3.469 (3) 159