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access1-Methyl-2,6-cis-distyrylpiperidine
aDepartment of Pharmaceutical Sciences, College of Pharmacy, University of Kentucky, Lexington, KY 40536, USA, and bDepartment of Chemistry, University of Kentucky, Lexington, KY 40536, USA
*Correspondence e-mail: pcrooks@email.uky.edu
The complete molecule of the title compound, C22H25N, is generated by crystallographic mirror symmetry, with two C atoms and the N atom lying on the mirror plane. The central ring adopts a chair conformation and the dihedral angle between the aromatic rings is 56.69 (4)°.
![[Scheme 1]](hg2598scheme1.gif)
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 1998![[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]](../../../../../../logos/arrows/e_arr.gif "Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.")
); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and local procedures.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536809049617/hg2598sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809049617/hg2598Isup2.hkl
The title compound was prepared from (-)-lobeline (Zheng et al., 2005). Crystal suitable for X-ray diffraction studies were obtained by slow evaporation of an hexanes/ethylacetate (10:1) solution at room temperature.
H atoms were found in difference Fourier maps and subsequently placed in idealized positions with constrained distances of 0.98 Å (RCH3), 0.99 Å (R2CH2), 1.00 Å (R3CH), 0.95 Å (R2CH), 0.93 Å (N—H), and with Uiso(H) values set to either 1.2Ueq or 1.5Ueq (RCH3) of the attached atom.
The SU of the torsion angle C6—C5—C2—H2 (-4.66 (14)°) is not directly available from the because H2 is in a calculated position, as determined by a riding model. It was set equal to the SU of torsion angles C6—C5—C2—N1 and C6—C5—C2—C3, both of which were 0.14°. This is valid because the coordinates of H2 are determined geometrically from the coordinates of atoms C2, C5, N1 and C3.
Data collection: COLLECT (Nonius, 1998); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in Siemens SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELX97 (Sheldrick, 2008) and local procedures.
![[Figure 1]](./hg2598fig1thm.gif) | Fig. 1. A view of the molecule with the atom numbering scheme (symmetry code A: x, -y+1/2,z). Displacement ellipsoids are drawn at the 50% probability level. |
| C22H25N | F(000) = 656 |
| Mr = 303.43 | Dx = 1.153 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 12455 reflections |
| a = 17.3766 (2) Å | θ = 1.0–27.5° |
| b = 18.1774 (6) Å | µ = 0.07 mm−1 |
| c = 5.5354 (7) Å | T = 173 K |
| V = 1748.3 (2) Å3 | Irregular block, colourless |
| Z = 4 | 0.40 × 0.25 × 0.20 mm |
| Nonius KappaCCD diffractometer | 1624 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.044 |
| Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
| Detector resolution: 18 pixels mm-1 | h = −22→22 |
| ω scans at fixed χ = 55° | k = −23→23 |
| 12693 measured reflections | l = −7→7 |
| 2077 independent reflections |
| 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)] = 0.051 | H-atom parameters constrained |
| wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0317P)2 + 0.526P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max = 0.001 |
| 2077 reflections | Δρmax = 0.19 e Å−3 |
| 110 parameters | Δρmin = −0.16 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0098 (16) |
| C22H25N | V = 1748.3 (2) Å3 |
| Mr = 303.43 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 17.3766 (2) Å | µ = 0.07 mm−1 |
| b = 18.1774 (6) Å | T = 173 K |
| c = 5.5354 (7) Å | 0.40 × 0.25 × 0.20 mm |
| Nonius KappaCCD diffractometer | 1624 reflections with I > 2σ(I) |
| 12693 measured reflections | Rint = 0.044 |
| 2077 independent reflections |
| R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
| wR(F2) = 0.105 | H-atom parameters constrained |
| S = 1.10 | Δρmax = 0.19 e Å−3 |
| 2077 reflections | Δρmin = −0.16 e Å−3 |
| 110 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.09202 (8) | 0.2500 | 0.1454 (3) | 0.0293 (4) | |
| C1 | 0.14851 (11) | 0.2500 | 0.3409 (4) | 0.0380 (5) | |
| H1A | 0.1238 | 0.2500 | 0.5016 | 0.046* | |
| H1B | 0.1809 | 0.2955 | 0.3259 | 0.046* | |
| C2 | 0.04374 (7) | 0.18311 (6) | 0.1549 (2) | 0.0291 (3) | |
| H2 | 0.0129 | 0.1845 | 0.3073 | 0.035* | |
| C3 | −0.01177 (8) | 0.18156 (7) | −0.0582 (2) | 0.0344 (3) | |
| H3A | 0.0180 | 0.1770 | −0.2100 | 0.041* | |
| H3B | −0.0453 | 0.1378 | −0.0443 | 0.041* | |
| C4 | −0.06143 (11) | 0.2500 | −0.0703 (4) | 0.0397 (5) | |
| H4A | −0.0912 | 0.2500 | −0.2228 | 0.048* | |
| H4B | −0.0983 | 0.2500 | 0.0659 | 0.048* | |
| C5 | 0.09154 (7) | 0.11450 (7) | 0.1566 (2) | 0.0302 (3) | |
| H5 | 0.1269 | 0.1079 | 0.0274 | 0.036* | |
| C6 | 0.08859 (7) | 0.06248 (7) | 0.3230 (2) | 0.0304 (3) | |
| H6 | 0.0547 | 0.0709 | 0.4547 | 0.036* | |
| C7 | 0.13201 (7) | −0.00733 (7) | 0.3274 (2) | 0.0280 (3) | |
| C8 | 0.12316 (7) | −0.05457 (7) | 0.5236 (2) | 0.0349 (3) | |
| H8 | 0.0885 | −0.0419 | 0.6497 | 0.042* | |
| C9 | 0.16422 (8) | −0.11997 (7) | 0.5374 (3) | 0.0412 (4) | |
| H9 | 0.1574 | −0.1517 | 0.6720 | 0.049* | |
| C10 | 0.21478 (8) | −0.13885 (7) | 0.3562 (3) | 0.0411 (4) | |
| H10 | 0.2430 | −0.1835 | 0.3655 | 0.049* | |
| C11 | 0.22423 (8) | −0.09261 (7) | 0.1615 (3) | 0.0386 (4) | |
| H11 | 0.2591 | −0.1055 | 0.0363 | 0.046* | |
| C12 | 0.18351 (7) | −0.02768 (7) | 0.1467 (2) | 0.0330 (3) | |
| H12 | 0.1907 | 0.0036 | 0.0111 | 0.040* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0269 (8) | 0.0241 (8) | 0.0369 (9) | 0.000 | −0.0038 (7) | 0.000 |
| C1 | 0.0347 (10) | 0.0307 (10) | 0.0486 (12) | 0.000 | −0.0101 (9) | 0.000 |
| C2 | 0.0291 (6) | 0.0251 (7) | 0.0332 (7) | −0.0001 (5) | 0.0003 (5) | −0.0005 (5) |
| C3 | 0.0362 (7) | 0.0278 (7) | 0.0391 (8) | −0.0025 (6) | −0.0059 (6) | −0.0027 (6) |
| C4 | 0.0369 (11) | 0.0326 (10) | 0.0496 (12) | 0.000 | −0.0143 (9) | 0.000 |
| C5 | 0.0289 (6) | 0.0273 (7) | 0.0345 (7) | −0.0013 (5) | 0.0019 (6) | −0.0016 (6) |
| C6 | 0.0279 (6) | 0.0297 (7) | 0.0334 (7) | −0.0020 (5) | 0.0010 (5) | −0.0031 (6) |
| C7 | 0.0254 (6) | 0.0242 (6) | 0.0342 (7) | −0.0038 (5) | −0.0053 (5) | −0.0012 (5) |
| C8 | 0.0314 (7) | 0.0371 (7) | 0.0361 (8) | −0.0054 (6) | 0.0003 (6) | 0.0011 (6) |
| C9 | 0.0450 (8) | 0.0315 (7) | 0.0471 (9) | −0.0099 (6) | −0.0089 (7) | 0.0125 (7) |
| C10 | 0.0385 (8) | 0.0220 (7) | 0.0628 (10) | 0.0007 (6) | −0.0101 (7) | −0.0027 (7) |
| C11 | 0.0373 (8) | 0.0303 (7) | 0.0482 (9) | −0.0008 (6) | 0.0012 (7) | −0.0079 (7) |
| C12 | 0.0362 (7) | 0.0281 (7) | 0.0348 (7) | −0.0031 (6) | −0.0005 (6) | 0.0015 (6) |
| N1—C1 | 1.461 (2) | C5—H5 | 0.9500 |
| N1—C2i | 1.4781 (14) | C6—C7 | 1.4765 (17) |
| N1—C2 | 1.4781 (14) | C6—H6 | 0.9500 |
| C1—H1A | 0.9877 | C7—C12 | 1.3922 (17) |
| C1—H1B | 1.0042 | C7—C8 | 1.3930 (18) |
| C2—C5 | 1.4984 (16) | C8—C9 | 1.3885 (19) |
| C2—C3 | 1.5238 (17) | C8—H8 | 0.9500 |
| C2—H2 | 1.0000 | C9—C10 | 1.377 (2) |
| C3—C4 | 1.5155 (16) | C9—H9 | 0.9500 |
| C3—H3A | 0.9900 | C10—C11 | 1.3765 (19) |
| C3—H3B | 0.9900 | C10—H10 | 0.9500 |
| C4—C3i | 1.5154 (16) | C11—C12 | 1.3785 (18) |
| C4—H4A | 0.9900 | C11—H11 | 0.9500 |
| C4—H4B | 0.9900 | C12—H12 | 0.9500 |
| C5—C6 | 1.3210 (17) | ||
| C1—N1—C2i | 110.79 (9) | C6—C5—C2 | 125.35 (12) |
| C1—N1—C2 | 110.79 (9) | C6—C5—H5 | 117.3 |
| C2i—N1—C2 | 110.68 (13) | C2—C5—H5 | 117.3 |
| N1—C1—H1A | 112.1 | C5—C6—C7 | 127.36 (12) |
| N1—C1—H1B | 108.4 | C5—C6—H6 | 116.3 |
| H1A—C1—H1B | 108.5 | C7—C6—H6 | 116.3 |
| N1—C2—C5 | 111.73 (10) | C12—C7—C8 | 117.85 (12) |
| N1—C2—C3 | 110.30 (11) | C12—C7—C6 | 123.03 (11) |
| C5—C2—C3 | 109.90 (10) | C8—C7—C6 | 119.10 (12) |
| N1—C2—H2 | 108.3 | C9—C8—C7 | 120.93 (13) |
| C5—C2—H2 | 108.3 | C9—C8—H8 | 119.5 |
| C3—C2—H2 | 108.3 | C7—C8—H8 | 119.5 |
| C4—C3—C2 | 112.31 (11) | C10—C9—C8 | 120.09 (13) |
| C4—C3—H3A | 109.1 | C10—C9—H9 | 120.0 |
| C2—C3—H3A | 109.1 | C8—C9—H9 | 120.0 |
| C4—C3—H3B | 109.1 | C11—C10—C9 | 119.61 (13) |
| C2—C3—H3B | 109.1 | C11—C10—H10 | 120.2 |
| H3A—C3—H3B | 107.9 | C9—C10—H10 | 120.2 |
| C3i—C4—C3 | 110.34 (15) | C10—C11—C12 | 120.55 (13) |
| C3i—C4—H4A | 109.6 | C10—C11—H11 | 119.7 |
| C3—C4—H4A | 109.6 | C12—C11—H11 | 119.7 |
| C3i—C4—H4B | 109.6 | C11—C12—C7 | 120.97 (12) |
| C3—C4—H4B | 109.6 | C11—C12—H12 | 119.5 |
| H4A—C4—H4B | 108.1 | C7—C12—H12 | 119.5 |
| C1—N1—C2—C5 | −54.16 (15) | C5—C6—C7—C12 | −0.36 (19) |
| C2i—N1—C2—C5 | −177.47 (8) | C5—C6—C7—C8 | 177.82 (12) |
| C1—N1—C2—C3 | −176.71 (11) | C12—C7—C8—C9 | −0.28 (18) |
| C2i—N1—C2—C3 | 59.97 (16) | C6—C7—C8—C9 | −178.56 (11) |
| N1—C2—C3—C4 | −56.00 (15) | C7—C8—C9—C10 | 0.3 (2) |
| C5—C2—C3—C4 | −179.62 (12) | C8—C9—C10—C11 | −0.1 (2) |
| C2—C3—C4—C3i | 51.3 (2) | C9—C10—C11—C12 | 0.0 (2) |
| N1—C2—C5—C6 | 123.80 (14) | C10—C11—C12—C7 | −0.02 (19) |
| C3—C2—C5—C6 | −113.41 (14) | C8—C7—C12—C11 | 0.16 (18) |
| C2—C5—C6—C7 | 177.26 (11) | C6—C7—C12—C11 | 178.36 (11) |
| Symmetry code: (i) x, −y+1/2, z. |
Experimental details
| Crystal data | |
| Chemical formula | C22H25N |
| Mr | 303.43 |
| Crystal system, space group | Orthorhombic, Pnma |
| Temperature (K) | 173 |
| a, b, c (Å) | 17.3766 (2), 18.1774 (6), 5.5354 (7) |
| V (Å3) | 1748.3 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.07 |
| Crystal size (mm) | 0.40 × 0.25 × 0.20 |
| Data collection | |
| Diffractometer | Nonius KappaCCD diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 12693, 2077, 1624 |
| Rint | 0.044 |
| (sin θ/λ)max (Å−1) | 0.650 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.105, 1.10 |
| No. of reflections | 2077 |
| No. of parameters | 110 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.19, −0.16 |
Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in Siemens SHELXTL (Sheldrick, 2008), SHELX97 (Sheldrick, 2008) and local procedures.
| N1—C2 | 1.4781 (14) | C3—C4 | 1.5155 (16) |
| C1—N1—C2 | 110.79 (9) | ||
| C2i—N1—C2—C5 | −177.47 (8) | C5—C6—C7—C8 | 177.82 (12) |
| C5—C2—C3—C4 | −179.62 (12) |
| Symmetry code: (i) x, −y+1/2, z. |
Acknowledgements
This research was supported by National Institute of Health grants DA13519 and DA00399.
References
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zheng, G., Dwoskin, L. P., Deaciuc, A. G., Norrholm, S. D. & Crooks, P. A. (2005). J. Med. Chem. pp. 5551–5560. Web of Science CrossRef Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
1-Methyl-2,6-cis-distyrylpiperidine, C22H25N, is a des-oxygen lobeline derivative (Zheng et al., 2005). The molecular structure is illustrated in Fig. 1, while selected geometric parameters are given in Table 1. The piperidine ring of the molecule is in the chair conformation and the N-methyl group is bonded equatorially to the piperidine ring. The styryl side chains are attached equatorially to the piperidine ring on atom C2 (and by symmetry, C2A). The molecule is mirror symmetric, with atoms N1, C1 and C4 lying on the mirror plane (Table 1). The double bond and the phenyl ring of the styryl side chain are approximately coplanar, as evidenced by the C5—C6—C7—C8 torsion angle [177.82 (12)°]. Moreover, the double bond is also approximately coplanar with C2—H2, as evidenced by the torsion angle C6—C5—C2—H2 [-4.66 (14)°].