Acta Cryst. (2009). E65, o1216 [ doi:10.1107/S1600536809015785 ]
In the title compound, C15H15NO4, the n-methylpiperidone ring adopts a chair conformation and both five-membered rings adopt a twist conformation. An intramolecular O-H
O hydrogen bond is observed. Inversion-related molecules are linked into R22(10) dimers by pairs of O-HO hydrogen bonds. The crystal structure is further stabilized by C-HO hydrogen bonds.
A mixture of 1-methyl-4-piperidinone (0.2 g, 0.002 mol), ninhydrin (0.315 g, 0.002 mol) and sarcosine (0.156 g, 0.002 mol) in methanol (30 ml) was refluxed in a water bath for 10 h. After completion of the reaction as monitored by TLC, the excess solvent was removed under vacuum and the residue was subjected to flash column chromatography using petroleum ether-ethyl acetate mixture (8:2 v/v) as eluent to obtain crystals of title compound in 8% yield along with a other product (yield 13%, m.p. 447–448 K).
The H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C-H = 0.93–0.98 Å, O-H = 0.82 Å and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(Cmethyl,O).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ci2789fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity. |
![[Figure 2]](./ci2789fig2thm.gif)
| Fig. 2. Partial packing view down the b axis. Hydrogen bonds are shown as dashed lines. |
| C15H15NO4 | Z = 2 |
| Mr = 273.28 | F000 = 288 |
| Triclinic, P1 | Dx = 1.375 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.5616 (7) Å | Cell parameters from 25 reflections |
| b = 8.9033 (8) Å | θ = 2–25º |
| c = 10.8091 (11) Å | µ = 0.10 mm−1 |
| α = 72.764 (11)º | T = 293 K |
| β = 80.486 (12)º | Block, colourless |
| γ = 72.369 (11)º | 0.18 × 0.15 × 0.11 mm |
| V = 660.09 (11) Å3 |
| Nonius MACH-3 diffractometer | Rint = 0.010 |
| Radiation source: fine-focus sealed tube | θmax = 25.0º |
| Monochromator: graphite | θmin = 2.5º |
| T = 293 K | h = −1→8 |
| ω–2θ scans | k = −10→10 |
| Absorption correction: ψ scan (North et al., 1968) | l = −12→12 |
| Tmin = 0.982, Tmax = 0.989 | 2 standard reflections |
| 2890 measured reflections | every 60 min |
| 2316 independent reflections | intensity decay: none |
| 2025 reflections with I > 2σ(I) |
| 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)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0454P)2 + 0.1839P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max = 0.001 |
| 2316 reflections | Δρmax = 0.22 e Å−3 |
| 184 parameters | Δρmin = −0.23 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C15H15NO4 | γ = 72.369 (11)º |
| Mr = 273.28 | V = 660.09 (11) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.5616 (7) Å | Mo Kα |
| b = 8.9033 (8) Å | µ = 0.10 mm−1 |
| c = 10.8091 (11) Å | T = 293 K |
| α = 72.764 (11)º | 0.18 × 0.15 × 0.11 mm |
| β = 80.486 (12)º |
| Nonius MACH-3 diffractometer | 2025 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.010 |
| Tmin = 0.982, Tmax = 0.989 | 2 standard reflections |
| 2890 measured reflections | every 60 min |
| 2316 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.037 | 184 parameters |
| wR(F2) = 0.097 | H-atom parameters constrained |
| S = 1.11 | Δρmax = 0.22 e Å−3 |
| 2316 reflections | Δρmin = −0.23 e Å−3 |
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 | ||
| O1 | 0.29809 (15) | 0.41843 (13) | 0.00498 (10) | 0.0446 (3) | |
| O2 | −0.04087 (14) | 0.29519 (13) | 0.08496 (10) | 0.0421 (3) | |
| H2 | −0.1139 | 0.3846 | 0.0581 | 0.063* | |
| O3 | −0.02584 (16) | 0.06248 (14) | 0.30007 (11) | 0.0499 (3) | |
| H3 | −0.0724 | 0.0852 | 0.2313 | 0.075* | |
| N1 | 0.29935 (17) | 0.38335 (15) | 0.28995 (12) | 0.0388 (3) | |
| O4 | −0.19177 (16) | 0.40313 (16) | 0.45054 (11) | 0.0538 (3) | |
| C8 | 0.2679 (2) | 0.30815 (17) | 0.09849 (13) | 0.0353 (3) | |
| C4 | 0.2670 (2) | 0.26334 (19) | 0.41090 (14) | 0.0403 (3) | |
| H4A | 0.2445 | 0.3121 | 0.4832 | 0.048* | |
| H4B | 0.3768 | 0.1712 | 0.4252 | 0.048* | |
| C10 | 0.3067 (2) | 0.04870 (17) | 0.24458 (14) | 0.0372 (3) | |
| C7 | 0.07412 (19) | 0.30768 (16) | 0.17048 (13) | 0.0322 (3) | |
| C5 | 0.0984 (2) | 0.20371 (18) | 0.40485 (13) | 0.0375 (3) | |
| H5 | 0.0730 | 0.1229 | 0.4847 | 0.045* | |
| C6 | 0.1144 (2) | 0.14491 (16) | 0.28236 (13) | 0.0348 (3) | |
| C9 | 0.3957 (2) | 0.14516 (17) | 0.14346 (14) | 0.0372 (3) | |
| C1 | −0.0622 (2) | 0.35556 (19) | 0.37706 (14) | 0.0383 (3) | |
| C3 | 0.1375 (2) | 0.52059 (18) | 0.25385 (15) | 0.0406 (3) | |
| H3A | 0.1661 | 0.5959 | 0.1728 | 0.049* | |
| H3B | 0.0969 | 0.5788 | 0.3209 | 0.049* | |
| C2 | −0.0144 (2) | 0.44610 (17) | 0.23864 (13) | 0.0362 (3) | |
| H2A | −0.1220 | 0.5275 | 0.1970 | 0.043* | |
| C14 | 0.5784 (2) | 0.0851 (2) | 0.09741 (16) | 0.0486 (4) | |
| H14 | 0.6375 | 0.1503 | 0.0301 | 0.058* | |
| C11 | 0.3986 (2) | −0.11196 (19) | 0.30063 (17) | 0.0496 (4) | |
| H11 | 0.3394 | −0.1777 | 0.3674 | 0.059* | |
| C12 | 0.5804 (3) | −0.1720 (2) | 0.25488 (18) | 0.0565 (5) | |
| H12 | 0.6442 | −0.2794 | 0.2917 | 0.068* | |
| C13 | 0.6699 (2) | −0.0751 (2) | 0.15496 (19) | 0.0572 (5) | |
| H13 | 0.7927 | −0.1183 | 0.1263 | 0.069* | |
| C18 | 0.4702 (3) | 0.4293 (3) | 0.2839 (2) | 0.0624 (5) | |
| H18A | 0.4881 | 0.5036 | 0.2010 | 0.094* | |
| H18B | 0.5737 | 0.3334 | 0.2949 | 0.094* | |
| H18C | 0.4615 | 0.4811 | 0.3517 | 0.094* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0438 (6) | 0.0456 (6) | 0.0332 (5) | −0.0098 (5) | 0.0005 (4) | 0.0021 (5) |
| O2 | 0.0419 (6) | 0.0433 (6) | 0.0416 (6) | −0.0060 (5) | −0.0146 (5) | −0.0116 (5) |
| O3 | 0.0522 (7) | 0.0488 (6) | 0.0518 (7) | −0.0269 (5) | −0.0081 (5) | −0.0022 (5) |
| N1 | 0.0360 (7) | 0.0438 (7) | 0.0393 (7) | −0.0155 (5) | 0.0001 (5) | −0.0116 (5) |
| O4 | 0.0413 (6) | 0.0706 (8) | 0.0475 (7) | −0.0118 (6) | 0.0104 (5) | −0.0234 (6) |
| C8 | 0.0365 (8) | 0.0379 (7) | 0.0285 (7) | −0.0084 (6) | −0.0037 (6) | −0.0053 (6) |
| C4 | 0.0413 (8) | 0.0455 (8) | 0.0329 (7) | −0.0085 (6) | −0.0075 (6) | −0.0095 (6) |
| C10 | 0.0422 (8) | 0.0343 (7) | 0.0341 (7) | −0.0068 (6) | −0.0073 (6) | −0.0090 (6) |
| C7 | 0.0320 (7) | 0.0335 (7) | 0.0289 (7) | −0.0067 (6) | −0.0057 (5) | −0.0053 (6) |
| C5 | 0.0396 (8) | 0.0413 (8) | 0.0268 (7) | −0.0130 (6) | 0.0003 (6) | −0.0013 (6) |
| C6 | 0.0369 (8) | 0.0322 (7) | 0.0338 (7) | −0.0120 (6) | −0.0039 (6) | −0.0030 (6) |
| C9 | 0.0378 (8) | 0.0387 (8) | 0.0326 (7) | −0.0050 (6) | −0.0052 (6) | −0.0101 (6) |
| C1 | 0.0350 (8) | 0.0468 (8) | 0.0360 (8) | −0.0141 (6) | 0.0002 (6) | −0.0135 (6) |
| C3 | 0.0491 (9) | 0.0361 (8) | 0.0370 (8) | −0.0128 (7) | −0.0008 (6) | −0.0100 (6) |
| C2 | 0.0349 (7) | 0.0354 (7) | 0.0339 (7) | −0.0028 (6) | −0.0053 (6) | −0.0080 (6) |
| C14 | 0.0396 (8) | 0.0557 (10) | 0.0453 (9) | −0.0037 (7) | −0.0015 (7) | −0.0160 (8) |
| C11 | 0.0600 (10) | 0.0342 (8) | 0.0482 (9) | −0.0044 (7) | −0.0111 (8) | −0.0064 (7) |
| C12 | 0.0617 (11) | 0.0404 (9) | 0.0592 (11) | 0.0085 (8) | −0.0191 (9) | −0.0161 (8) |
| C13 | 0.0442 (9) | 0.0592 (11) | 0.0625 (11) | 0.0096 (8) | −0.0102 (8) | −0.0286 (9) |
| C18 | 0.0456 (10) | 0.0723 (12) | 0.0787 (13) | −0.0281 (9) | 0.0013 (9) | −0.0244 (10) |
| O1—C8 | 1.2285 (17) | C5—C1 | 1.509 (2) |
| O2—C7 | 1.4171 (16) | C5—C6 | 1.537 (2) |
| O2—H2 | 0.82 | C5—H5 | 0.98 |
| O3—C6 | 1.4219 (17) | C9—C14 | 1.387 (2) |
| O3—H3 | 0.82 | C1—C2 | 1.517 (2) |
| N1—C3 | 1.453 (2) | C3—C2 | 1.541 (2) |
| N1—C18 | 1.455 (2) | C3—H3A | 0.97 |
| N1—C4 | 1.4613 (19) | C3—H3B | 0.97 |
| O4—C1 | 1.2088 (18) | C2—H2A | 0.98 |
| C8—C9 | 1.471 (2) | C14—C13 | 1.385 (3) |
| C8—C7 | 1.5419 (19) | C14—H14 | 0.93 |
| C4—C5 | 1.539 (2) | C11—C12 | 1.381 (3) |
| C4—H4A | 0.97 | C11—H11 | 0.93 |
| C4—H4B | 0.97 | C12—C13 | 1.388 (3) |
| C10—C11 | 1.386 (2) | C12—H12 | 0.93 |
| C10—C9 | 1.391 (2) | C13—H13 | 0.93 |
| C10—C6 | 1.507 (2) | C18—H18A | 0.96 |
| C7—C2 | 1.5443 (19) | C18—H18B | 0.96 |
| C7—C6 | 1.5720 (18) | C18—H18C | 0.96 |
| C7—O2—H2 | 109.5 | C14—C9—C8 | 128.62 (14) |
| C6—O3—H3 | 109.5 | C10—C9—C8 | 109.95 (13) |
| C3—N1—C18 | 114.32 (13) | O4—C1—C5 | 128.54 (14) |
| C3—N1—C4 | 113.97 (12) | O4—C1—C2 | 126.94 (14) |
| C18—N1—C4 | 112.86 (13) | C5—C1—C2 | 104.23 (11) |
| O1—C8—C9 | 126.53 (13) | N1—C3—C2 | 105.67 (11) |
| O1—C8—C7 | 124.00 (12) | N1—C3—H3A | 110.6 |
| C9—C8—C7 | 108.44 (12) | C2—C3—H3A | 110.6 |
| N1—C4—C5 | 110.50 (11) | N1—C3—H3B | 110.6 |
| N1—C4—H4A | 109.6 | C2—C3—H3B | 110.6 |
| C5—C4—H4A | 109.6 | H3A—C3—H3B | 108.7 |
| N1—C4—H4B | 109.6 | C1—C2—C3 | 103.05 (11) |
| C5—C4—H4B | 109.6 | C1—C2—C7 | 103.33 (11) |
| H4A—C4—H4B | 108.1 | C3—C2—C7 | 109.41 (11) |
| C11—C10—C9 | 120.35 (15) | C1—C2—H2A | 113.4 |
| C11—C10—C6 | 128.39 (14) | C3—C2—H2A | 113.4 |
| C9—C10—C6 | 111.20 (12) | C7—C2—H2A | 113.4 |
| O2—C7—C8 | 108.50 (11) | C13—C14—C9 | 117.82 (16) |
| O2—C7—C2 | 114.39 (11) | C13—C14—H14 | 121.1 |
| C8—C7—C2 | 115.40 (12) | C9—C14—H14 | 121.1 |
| O2—C7—C6 | 108.69 (11) | C12—C11—C10 | 118.30 (16) |
| C8—C7—C6 | 103.21 (11) | C12—C11—H11 | 120.8 |
| C2—C7—C6 | 105.84 (11) | C10—C11—H11 | 120.8 |
| C1—C5—C6 | 100.91 (11) | C11—C12—C13 | 121.32 (15) |
| C1—C5—C4 | 105.49 (12) | C11—C12—H12 | 119.3 |
| C6—C5—C4 | 112.08 (11) | C13—C12—H12 | 119.3 |
| C1—C5—H5 | 112.5 | C14—C13—C12 | 120.77 (16) |
| C6—C5—H5 | 112.5 | C14—C13—H13 | 119.6 |
| C4—C5—H5 | 112.5 | C12—C13—H13 | 119.6 |
| O3—C6—C10 | 114.30 (12) | N1—C18—H18A | 109.5 |
| O3—C6—C5 | 106.98 (11) | N1—C18—H18B | 109.5 |
| C10—C6—C5 | 114.94 (12) | H18A—C18—H18B | 109.5 |
| O3—C6—C7 | 111.58 (11) | N1—C18—H18C | 109.5 |
| C10—C6—C7 | 104.97 (11) | H18A—C18—H18C | 109.5 |
| C5—C6—C7 | 103.62 (11) | H18B—C18—H18C | 109.5 |
| C14—C9—C10 | 121.43 (14) | ||
| C3—N1—C4—C5 | 54.45 (16) | C6—C10—C9—C14 | 176.26 (14) |
| C18—N1—C4—C5 | −172.98 (13) | C11—C10—C9—C8 | 178.38 (14) |
| O1—C8—C7—O2 | 66.57 (17) | C6—C10—C9—C8 | −4.31 (17) |
| C9—C8—C7—O2 | −102.49 (12) | O1—C8—C9—C14 | 4.9 (3) |
| O1—C8—C7—C2 | −63.28 (18) | C7—C8—C9—C14 | 173.60 (15) |
| C9—C8—C7—C2 | 127.66 (12) | O1—C8—C9—C10 | −174.49 (14) |
| O1—C8—C7—C6 | −178.24 (13) | C7—C8—C9—C10 | −5.78 (16) |
| C9—C8—C7—C6 | 12.70 (14) | C6—C5—C1—O4 | 138.05 (16) |
| N1—C4—C5—C1 | −56.97 (15) | C4—C5—C1—O4 | −105.16 (17) |
| N1—C4—C5—C6 | 51.96 (16) | C6—C5—C1—C2 | −47.81 (13) |
| C11—C10—C6—O3 | −48.1 (2) | C4—C5—C1—C2 | 68.98 (13) |
| C9—C10—C6—O3 | 134.84 (13) | C18—N1—C3—C2 | 168.31 (13) |
| C11—C10—C6—C5 | 76.15 (19) | C4—N1—C3—C2 | −59.82 (15) |
| C9—C10—C6—C5 | −100.88 (14) | O4—C1—C2—C3 | 98.33 (17) |
| C11—C10—C6—C7 | −170.70 (15) | C5—C1—C2—C3 | −75.95 (13) |
| C9—C10—C6—C7 | 12.27 (15) | O4—C1—C2—C7 | −147.76 (15) |
| C1—C5—C6—O3 | −80.03 (13) | C5—C1—C2—C7 | 37.97 (14) |
| C4—C5—C6—O3 | 168.14 (11) | N1—C3—C2—C1 | 69.03 (14) |
| C1—C5—C6—C10 | 151.91 (12) | N1—C3—C2—C7 | −40.39 (14) |
| C4—C5—C6—C10 | 40.09 (16) | O2—C7—C2—C1 | 106.41 (13) |
| C1—C5—C6—C7 | 37.97 (13) | C8—C7—C2—C1 | −126.65 (12) |
| C4—C5—C6—C7 | −73.85 (14) | C6—C7—C2—C1 | −13.22 (14) |
| O2—C7—C6—O3 | −23.90 (15) | O2—C7—C2—C3 | −144.35 (12) |
| C8—C7—C6—O3 | −138.96 (12) | C8—C7—C2—C3 | −17.42 (15) |
| C2—C7—C6—O3 | 99.41 (13) | C6—C7—C2—C3 | 96.02 (13) |
| O2—C7—C6—C10 | 100.42 (12) | C10—C9—C14—C13 | 0.3 (2) |
| C8—C7—C6—C10 | −14.64 (14) | C8—C9—C14—C13 | −178.97 (15) |
| C2—C7—C6—C10 | −136.28 (11) | C9—C10—C11—C12 | 1.0 (2) |
| O2—C7—C6—C5 | −138.66 (11) | C6—C10—C11—C12 | −175.81 (15) |
| C8—C7—C6—C5 | 106.28 (12) | C10—C11—C12—C13 | −0.3 (3) |
| C2—C7—C6—C5 | −15.36 (14) | C9—C14—C13—C12 | 0.4 (3) |
| C11—C10—C9—C14 | −1.1 (2) | C11—C12—C13—C14 | −0.4 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O2 | 0.82 | 2.11 | 2.6080 (15) | 119 |
| O2—H2···O1i | 0.82 | 1.90 | 2.7168 (15) | 175 |
| C2—H2A···O1i | 0.98 | 2.59 | 3.3778 (18) | 137 |
| C18—H18A···O1ii | 0.96 | 2.57 | 3.432 (2) | 149 |
| C5—H5···O3iii | 0.98 | 2.46 | 3.4381 (18) | 173 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O2 | 0.82 | 2.11 | 2.6080 (15) | 119 |
| O2—H2···O1i | 0.82 | 1.90 | 2.7168 (15) | 175 |
| C2—H2A···O1i | 0.98 | 2.59 | 3.3778 (18) | 137 |
| C18—H18A···O1ii | 0.96 | 2.57 | 3.432 (2) | 149 |
| C5—H5···O3iii | 0.98 | 2.46 | 3.4381 (18) | 173 |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x, −y, −z+1. |
JS and SN thank the Management of The Madura College, Madurai, for their constant support.
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Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany.
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The piperidine ring is a distinct structural feature of a variety of alkaloid natural products and drug candidates. Watson et al. (2000) observed that during the past decade there were thousands of piperidine compounds mentioned in clinical and preclinical studies. Piperidinones, though relatively less prominent, have also been regarded as precursors of a host of biologically active compounds and natural alkaloids, prior to their conversion to piperidines. Ninhydrin is a chemical used to detect ammonia or primary and secondary amines.
In the molecule of the title compound, (Fig. 1), the six-membered ring A (N1/C4/C5/C1/C2/C3), and the five membered rings B (C1/C2/C7/C6/C5) and C(C6-C10) are not planar. Rings B and C both adopt twist conformations, as indicated by Cremer & Pople (1975) puckering parameters Q = 0.455 (2) Å and Φ = 160.4 (2)° for ring B, and Q = 0.149 (2) Å and Φ = 21.6 (6)° for ring C. Ring A adopts a chair conformation.
In the crystal structure, the molecules are linked to form dimers by intermolecular O—H···O hydrogen bonds (Table 1), generating a graph set motif of R22(10) (Fig.2). In addition, the structure is stabilized by C—H···O and van der Waals interactions.