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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1505.
Published online 2010 May 29. doi:  10.1107/S1600536810018490
PMCID: PMC2979406

1-Formyl-t-3,t-5-dimethyl-r-2,c-6-diphenyl­piperidin-4-one

Abstract

In the title compound, C20H21NO2, the piperidine ring adopts a distorted boat conformation. The dihedral angle between the two phenyl rings is 61.33 (18)°. In the crystal, inter­molecular C—H(...)O inter­actions link the mol­ecules into zigzag C(5) chains running parallel to [100].

Related literature

For general background to piperidine derivatives, see: Perumal et al. (2001 [triangle]); Dimmock et al. (2001 [triangle]). For asymmetry parameters, see: Nardelli (1983 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For the synthesis, see: Jeyaraman et al. (1999 [triangle]).

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Object name is e-66-o1505-scheme1.jpg

Experimental

Crystal data

  • C20H21NO2
  • M r = 307.38
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1505-efi1.jpg
  • a = 7.4303 (4) Å
  • b = 15.3567 (6) Å
  • c = 29.6732 (13) Å
  • V = 3385.9 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 292 K
  • 0.22 × 0.19 × 0.16 mm

Data collection

  • Bruker SMART APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.983, T max = 0.988
  • 16882 measured reflections
  • 4198 independent reflections
  • 2097 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.194
  • S = 1.02
  • 4198 reflections
  • 213 parameters
  • 25 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018490/ci5087sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018490/ci5087Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

KR thanks the TBI Consultancy, University of Madras, India, for the data collection and the management of Kandaswami Kandar’s College, Velur, Namakkal, Tamilnadu, India, for the encouragement to pursue the programme.

supplementary crystallographic information

Comment

Piperidine derivatives are valued heterocyclic compounds in the field of medicinal chemistry. Piperidin-4-ones are reported to possess analgesic, anti-inflammatory, central nervous system (CNS), local anaesthetic, anticancer and antimicrobial activities (Perumal et al., 2001; Dimmock et al., 2001). The crystallographic study of the title compound has been carried out to establish the molecular structure.

In the title molecule (Fig. 1), the piperidine ring adopts a distorted boat conformation; the puckering (Cremer & Pople, 1975) and asymmetry parameters (Nardelli, 1983) are: q2 = 0.637 (3) Å, q3 = -0.052 (3) Å, [var phi]2 = 245.5 (2)° and Δs(C2 & C5) = 3.5 (2)°. The C8—C13 and C16—C21 phenyl rings are in axial [C4—C3—C2—C8 = 75.6 (3)°] and equatorial [C4—C5—C6—C16 = -166.8 (2)°] orientations, respectively. The methyl groups attached to atoms C3 and C5 of the piperidine ring are in axial and equatorial orientations [N1—C2—C3—C14 = 69.9 (2)° and N1—C6—C5—C15 = -168.1 (2)°]. The sum of bond angles around atom N1 (359.5°) of the piperidine ring is in accordance with sp2 hybridization.

Atom C6 at (x, y, z) acts as a hydrogen-bond donor to atom O2 of the molecule at (x-1/2, y, 1/2-z) forming a zigzag C(5) chain (Bernstein et al., 1995) running along the a axis, as shown in Fig. 2.

Experimental

An ice-cold solution of acetic-formic anhydride prepared from acetic anhydride (10 ml) and 85% formic acid (5 ml) was added slowly to a cold solution of r-2,c-6-diphenyl-t-3,t-5-dimethyl piperidin-4-one (1.395 g, 5 mmol) in benzene (30 ml). The reaction mixture was stirred at room temperature for 5 h. The organic layer was separated, dried over anhydrous Na2SO4 and concentrated. The resulting mass was purified and crystallized from benzene- petroleum ether (333-335 K) in the ratio 1:1 (Jeyaraman et al., 1999).

Refinement

Atom H7 was located in a difference map and its positional parameters were refined. The remaining H atoms were positioned geometrically (C–H =0.93-0.98 Å, ) and allowed to ride on their parent atoms, with 1.5Ueq(C) for methyl and 1.2 Ueq(C) for other H atoms. The Uij parameters of atoms O1, C7, C10 and C11 were restrained to an approximate isotropic behaviour.

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
Fig. 2.
The crystal packing of the molecules viewed down the b axis. H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C20H21NO2F(000) = 1312
Mr = 307.38Dx = 1.206 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1246 reflections
a = 7.4303 (4) Åθ = 1.4–28.4°
b = 15.3567 (6) ŵ = 0.08 mm1
c = 29.6732 (13) ÅT = 292 K
V = 3385.9 (3) Å3Block, colourless
Z = 80.22 × 0.19 × 0.16 mm

Data collection

Bruker SMART APEXII area-detector diffractometer4198 independent reflections
Radiation source: fine-focus sealed tube2097 reflections with I > 2σ(I)
graphiteRint = 0.030
ω and [var phi] scansθmax = 28.4°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −9→6
Tmin = 0.983, Tmax = 0.988k = −20→18
16882 measured reflectionsl = −39→38

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.194H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0741P)2 + 1.1948P] where P = (Fo2 + 2Fc2)/3
4198 reflections(Δ/σ)max = 0.001
213 parametersΔρmax = 0.37 e Å3
25 restraintsΔρmin = −0.22 e Å3

Special details

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.0192 (4)0.2060 (2)0.13459 (14)0.1697 (16)
O20.6395 (3)0.38855 (13)0.21978 (6)0.0841 (6)
N10.2046 (3)0.31856 (13)0.14813 (8)0.0690 (6)
C20.3721 (3)0.27494 (15)0.13546 (9)0.0645 (7)
H20.34260.21320.13170.077*
C30.5024 (3)0.28034 (15)0.17521 (8)0.0565 (6)
H30.62040.25960.16510.068*
C40.5235 (3)0.37170 (15)0.19238 (8)0.0563 (6)
C50.3986 (3)0.44063 (14)0.17429 (8)0.0535 (6)
H50.44440.45700.14450.064*
C60.2059 (3)0.40703 (16)0.16730 (8)0.0586 (6)
H60.14980.40340.19710.070*
C70.0458 (5)0.2769 (3)0.14840 (17)0.1186 (15)
C80.4415 (4)0.30662 (16)0.09006 (9)0.0715 (8)
C90.3332 (6)0.2922 (2)0.05318 (12)0.1179 (14)
H90.22430.26320.05690.141*
C100.3834 (9)0.3199 (3)0.01118 (15)0.1455 (18)
H100.31060.3078−0.01350.175*
C110.5382 (9)0.3649 (3)0.00538 (13)0.1369 (17)
H110.56790.3869−0.02290.164*
C120.6510 (6)0.3778 (3)0.04115 (13)0.1199 (14)
H120.76010.40650.03710.144*
C130.6019 (5)0.3479 (2)0.08344 (10)0.0854 (9)
H130.67940.35600.10770.103*
C140.4401 (4)0.22289 (18)0.21443 (10)0.0781 (8)
H14A0.52360.22810.23900.117*
H14B0.43480.16330.20470.117*
H14C0.32290.24130.22420.117*
C150.3989 (4)0.52323 (17)0.20290 (10)0.0779 (8)
H15A0.33430.51280.23040.117*
H15B0.34180.56950.18650.117*
H15C0.52070.53930.20980.117*
C160.0934 (3)0.46917 (17)0.13948 (9)0.0627 (6)
C17−0.0611 (4)0.50498 (19)0.15754 (11)0.0781 (8)
H17−0.09500.48950.18660.094*
C18−0.1656 (4)0.5623 (2)0.13407 (17)0.1041 (12)
H18−0.26860.58550.14720.125*
C19−0.1192 (6)0.5849 (2)0.09201 (18)0.1146 (14)
H19−0.19020.62410.07600.138*
C200.0328 (6)0.5506 (2)0.07227 (12)0.1109 (12)
H200.06380.56620.04300.133*
C210.1400 (5)0.4924 (2)0.09632 (10)0.0881 (9)
H210.24320.46940.08320.106*
H7−0.076 (5)0.287 (2)0.1562 (11)0.106*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.113 (2)0.099 (2)0.298 (4)−0.0455 (18)−0.089 (2)0.053 (2)
O20.0795 (13)0.0781 (13)0.0947 (14)−0.0123 (10)−0.0379 (11)−0.0045 (10)
N10.0443 (11)0.0572 (12)0.1055 (16)−0.0146 (10)−0.0220 (11)0.0253 (11)
C20.0677 (16)0.0427 (12)0.0832 (17)−0.0081 (12)−0.0297 (13)0.0010 (12)
C30.0484 (12)0.0515 (13)0.0695 (14)−0.0012 (11)−0.0139 (11)0.0017 (11)
C40.0486 (12)0.0571 (14)0.0631 (14)−0.0099 (11)−0.0099 (11)0.0045 (11)
C50.0527 (12)0.0480 (12)0.0597 (13)−0.0046 (10)0.0025 (10)0.0044 (10)
C60.0474 (12)0.0678 (15)0.0606 (13)0.0004 (11)0.0032 (10)0.0163 (12)
C70.085 (2)0.078 (2)0.193 (4)−0.038 (2)−0.057 (3)0.057 (2)
C80.096 (2)0.0484 (13)0.0705 (17)0.0024 (14)−0.0257 (15)−0.0083 (12)
C90.172 (4)0.095 (2)0.087 (2)−0.018 (2)−0.062 (2)0.0030 (19)
C100.222 (5)0.127 (4)0.087 (3)−0.001 (4)−0.060 (3)−0.003 (2)
C110.222 (5)0.120 (3)0.069 (2)0.018 (3)0.006 (3)−0.008 (2)
C120.153 (4)0.123 (3)0.083 (2)−0.004 (3)0.030 (3)−0.015 (2)
C130.101 (2)0.089 (2)0.0661 (17)−0.0029 (19)0.0057 (16)−0.0164 (15)
C140.0777 (18)0.0679 (17)0.0887 (19)−0.0093 (14)−0.0188 (15)0.0189 (14)
C150.094 (2)0.0595 (16)0.0801 (18)0.0007 (15)0.0063 (16)−0.0074 (14)
C160.0525 (13)0.0661 (15)0.0696 (15)0.0061 (12)−0.0013 (11)0.0106 (12)
C170.0534 (15)0.0730 (18)0.108 (2)0.0041 (14)0.0022 (15)0.0017 (16)
C180.0604 (18)0.070 (2)0.182 (4)0.0121 (16)−0.019 (2)0.005 (2)
C190.095 (3)0.075 (2)0.174 (4)0.011 (2)−0.054 (3)0.029 (3)
C200.137 (3)0.098 (3)0.097 (2)0.008 (3)−0.023 (2)0.037 (2)
C210.097 (2)0.089 (2)0.0784 (18)0.0259 (17)0.0042 (16)0.0265 (16)

Geometric parameters (Å, °)

O1—C71.180 (5)C10—H100.93
O2—C41.213 (3)C11—C121.367 (6)
N1—C71.342 (4)C11—H110.93
N1—C21.462 (3)C12—C131.385 (4)
N1—C61.473 (3)C12—H120.93
C2—C81.522 (4)C13—H130.93
C2—C31.528 (3)C14—H14A0.96
C2—H20.98C14—H14B0.96
C3—C41.501 (3)C14—H14C0.96
C3—C141.532 (3)C15—H15A0.96
C3—H30.98C15—H15B0.96
C4—C51.507 (3)C15—H15C0.96
C5—C151.526 (3)C16—C211.374 (4)
C5—C61.536 (3)C16—C171.381 (4)
C5—H50.98C17—C181.365 (4)
C6—C161.513 (3)C17—H170.93
C6—H60.98C18—C191.341 (5)
C7—H70.95 (4)C18—H180.93
C8—C131.363 (4)C19—C201.378 (5)
C8—C91.376 (4)C19—H190.93
C9—C101.369 (6)C20—C211.393 (4)
C9—H90.93C20—H200.93
C10—C111.353 (7)C21—H210.93
C7—N1—C2122.1 (3)C9—C10—H10119.8
C7—N1—C6116.3 (3)C10—C11—C12119.8 (4)
C2—N1—C6121.11 (17)C10—C11—H11120.1
N1—C2—C8111.7 (2)C12—C11—H11120.1
N1—C2—C3108.4 (2)C11—C12—C13119.6 (4)
C8—C2—C3116.8 (2)C11—C12—H12120.2
N1—C2—H2106.4C13—C12—H12120.2
C8—C2—H2106.4C8—C13—C12121.0 (3)
C3—C2—H2106.4C8—C13—H13119.5
C4—C3—C2112.28 (19)C12—C13—H13119.5
C4—C3—C14108.2 (2)C3—C14—H14A109.5
C2—C3—C14111.3 (2)C3—C14—H14B109.5
C4—C3—H3108.3H14A—C14—H14B109.5
C2—C3—H3108.3C3—C14—H14C109.5
C14—C3—H3108.3H14A—C14—H14C109.5
O2—C4—C3120.1 (2)H14B—C14—H14C109.5
O2—C4—C5121.8 (2)C5—C15—H15A109.5
C3—C4—C5118.12 (19)C5—C15—H15B109.5
C4—C5—C15112.6 (2)H15A—C15—H15B109.5
C4—C5—C6112.73 (18)C5—C15—H15C109.5
C15—C5—C6110.8 (2)H15A—C15—H15C109.5
C4—C5—H5106.7H15B—C15—H15C109.5
C15—C5—H5106.7C21—C16—C17117.9 (3)
C6—C5—H5106.7C21—C16—C6122.2 (2)
N1—C6—C16111.6 (2)C17—C16—C6119.9 (2)
N1—C6—C5111.58 (19)C18—C17—C16122.1 (3)
C16—C6—C5112.11 (19)C18—C17—H17118.9
N1—C6—H6107.1C16—C17—H17118.9
C16—C6—H6107.1C19—C18—C17119.7 (3)
C5—C6—H6107.1C19—C18—H18120.1
O1—C7—N1125.8 (5)C17—C18—H18120.1
O1—C7—H794 (2)C18—C19—C20120.5 (3)
N1—C7—H7140 (2)C18—C19—H19119.8
C13—C8—C9118.1 (3)C20—C19—H19119.8
C13—C8—C2124.9 (2)C19—C20—C21119.8 (3)
C9—C8—C2117.0 (3)C19—C20—H20120.1
C10—C9—C8121.0 (4)C21—C20—H20120.1
C10—C9—H9119.5C16—C21—C20120.0 (3)
C8—C9—H9119.5C16—C21—H21120.0
C11—C10—C9120.4 (4)C20—C21—H21120.0
C11—C10—H10119.8
C7—N1—C2—C8109.2 (3)C6—N1—C7—O1−179.9 (4)
C6—N1—C2—C8−79.4 (3)N1—C2—C8—C13117.9 (3)
C7—N1—C2—C3−120.7 (3)C3—C2—C8—C13−7.7 (4)
C6—N1—C2—C350.6 (3)N1—C2—C8—C9−62.1 (3)
N1—C2—C3—C4−51.5 (3)C3—C2—C8—C9172.3 (3)
C8—C2—C3—C475.6 (3)C13—C8—C9—C10−1.2 (5)
N1—C2—C3—C1469.9 (2)C2—C8—C9—C10178.8 (4)
C8—C2—C3—C14−162.9 (2)C8—C9—C10—C11−2.3 (7)
C2—C3—C4—O2−170.3 (2)C9—C10—C11—C124.3 (8)
C14—C3—C4—O266.4 (3)C10—C11—C12—C13−2.7 (7)
C2—C3—C4—C59.2 (3)C9—C8—C13—C122.7 (5)
C14—C3—C4—C5−114.1 (2)C2—C8—C13—C12−177.3 (3)
O2—C4—C5—C15−16.0 (3)C11—C12—C13—C8−0.8 (6)
C3—C4—C5—C15164.5 (2)N1—C6—C16—C21−66.4 (3)
O2—C4—C5—C6−142.4 (2)C5—C6—C16—C2159.5 (3)
C3—C4—C5—C638.2 (3)N1—C6—C16—C17114.1 (3)
C7—N1—C6—C16−65.6 (3)C5—C6—C16—C17−120.0 (3)
C2—N1—C6—C16122.6 (2)C21—C16—C17—C18−0.5 (4)
C7—N1—C6—C5168.1 (3)C6—C16—C17—C18179.0 (3)
C2—N1—C6—C5−3.7 (3)C16—C17—C18—C190.3 (5)
C4—C5—C6—N1−40.9 (3)C17—C18—C19—C200.2 (6)
C15—C5—C6—N1−168.1 (2)C18—C19—C20—C21−0.5 (6)
C4—C5—C6—C16−166.8 (2)C17—C16—C21—C200.1 (5)
C15—C5—C6—C1665.9 (3)C6—C16—C21—C20−179.4 (3)
C2—N1—C7—O1−8.2 (6)C19—C20—C21—C160.4 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.982.483.398 (3)156

Symmetry codes: (i) x−1/2, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5087).

References

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