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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1420.
Published online 2009 May 29. doi:  10.1107/S1600536809019357
PMCID: PMC2969687

r-2,c-6-Bis(4-methoxy­phenyl)-c-3,t-3-dimethyl-1-nitro­sopiperidin-4-one

Abstract

In the title compound, C21H24N2O4, the piperidine ring adopts a distorted boat conformation. The crystal structure is stabilized by C—H(...)π inter­actions involving one of the methoxy­phenyl rings.

Related literature

For the biological activity of piperidones, see: Dimmock et al. (1990 [triangle]); Mutus et al. (1989 [triangle]); Perumal et al. (2001 [triangle]). For ring conformations, see: Cremer & Pople (1975 [triangle]); Nardelli (1983 [triangle]).

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Object name is e-65-o1420-scheme1.jpg

Experimental

Crystal data

  • C21H24N2O4
  • M r = 368.42
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1420-efi1.jpg
  • a = 7.2540 (3) Å
  • b = 15.0469 (6) Å
  • c = 17.0741 (7) Å
  • V = 1863.64 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Bruker Kappa APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001 [triangle]) T min = 0.973, T max = 0.982
  • 24656 measured reflections
  • 3211 independent reflections
  • 2595 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.109
  • S = 1.03
  • 3211 reflections
  • 244 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [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: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019357/ci2805sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019357/ci2805Isup2.hkl

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

Acknowledgments

TK thanks Dr Babu Varghese, SAIF, IIT-Madras, Chennai, India, for his help with the data collection. SP thanks the UGC, India, for financial support.

supplementary crystallographic information

Comment

2,6-Disubstituted 4-piperidones are found to have various biological and pharmacological activities (Dimmock et al., 1990; Mutus et al., 1989). Piperidones are also reported to possess analgesic, anti-inflammatory, central nervous system (CNS), local anaesthetic, anticancer and antimicrobial activities (Perumal et al., 2001).

The piperidine ring adopts a distorted boat conformation, with puckering parameters (Cremer & Pople, 1975) q2 = 0.613 (2) Å, q3 = -0.123 (2) Å and [var phi]2 = 260.6 (2)° and the asymmetry parameters ΔCs(C2) = ΔCs(C5) = 21.7 (2)° (Nardelli, 1983). The C8—C13 and C16—C21 phenyl rings are oriented at angles of 88.04 (6)° and 82.38 (7)°, respectively, with the best plane (N1/C3/C4/C6) through the piperidine ring. The C14 methyl group is oriented axially [N1—C2—C3—C14 = 53.8 (2)°] while the C15 methyl group is oriented equatorially [N1—C2—C3—C15 = 173.3 (2)°] to the piperidinone ring. The sum of bond angles around N1 [358.1°] shows that the atom N1 is in sp2 hybridzed state. There is a delocalization between the lone pair of electrons and the hetero π-electrons of the nitroso group.

The packing of the molecules in the crystal is through C—H··· π interactions.

Experimental

To a solution of r-2,c-6-bis(4-methoxyphenyl)-c-3,t-3-dimethylpiperidin-4-one (1.69 g, 5 mmol) in chloroform (10 ml) was added with conc. HCl (1.5 ml) and water (1.5 ml) and while stirring, solid NaNO2 (0.84 g,12 mmol) was added in portions over the period of 0.5 h. The solution was stirred at room temperature for another 0.5 h. The organic layer was washed with water, saturated with aqueous NaHCO3 and dried over anhydrous Na2SO4. The resulting solution was concentrated and the residue was crystallized from ethanol.

Refinement

H atoms were positioned geometrically (C-H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq(C) for other H atoms. In the absence of significant anomalous scattering effects, Friedel pairs were averaged.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
Fig. 2.
Part of the crystal packing of the title compound, viewed approximately along the a axis. Dashed lines indicate C—H···π interactions. H atoms not involved in the interactions have been omitted.

Crystal data

C21H24N2O4F(000) = 784
Mr = 368.42Dx = 1.313 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3211 reflections
a = 7.2540 (3) Åθ = 2.4–30.5°
b = 15.0469 (6) ŵ = 0.09 mm1
c = 17.0741 (7) ÅT = 293 K
V = 1863.64 (13) Å3Block, colourless
Z = 40.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa-APEXII CCD area-detector diffractometer3211 independent reflections
Radiation source: fine-focus sealed tube2595 reflections with I > 2σ(I)
graphiteRint = 0.026
ω scansθmax = 30.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)h = −10→10
Tmin = 0.973, Tmax = 0.982k = −21→21
24656 measured reflectionsl = −24→24

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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0532P)2 + 0.2754P] where P = (Fo2 + 2Fc2)/3
3211 reflections(Δ/σ)max = 0.001
244 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.15 e Å3

Special details

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.

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

xyzUiso*/Ueq
N10.0483 (2)0.52808 (12)0.21105 (9)0.0433 (4)
C20.1305 (2)0.58054 (13)0.27489 (10)0.0417 (4)
H20.02760.60150.30720.050*
C30.2206 (3)0.66398 (14)0.23982 (11)0.0453 (4)
C40.3709 (3)0.63719 (14)0.18259 (11)0.0478 (4)
C50.3450 (3)0.54846 (14)0.14164 (11)0.0464 (4)
H5A0.42350.50540.16750.056*
H5B0.38980.55470.08840.056*
C60.1494 (3)0.50917 (13)0.13767 (10)0.0419 (4)
H60.08400.53920.09500.050*
N7−0.1331 (2)0.51769 (14)0.21570 (12)0.0589 (5)
C80.2461 (3)0.52025 (13)0.32719 (10)0.0413 (4)
C90.4369 (3)0.51945 (15)0.33242 (11)0.0461 (4)
H90.50480.55890.30200.055*
C100.5290 (3)0.46138 (15)0.38177 (12)0.0500 (5)
H100.65710.46200.38370.060*
C110.4317 (3)0.40259 (13)0.42807 (12)0.0484 (4)
C120.2405 (3)0.40122 (16)0.42284 (13)0.0562 (5)
H120.17300.36110.45280.067*
C130.1513 (3)0.45897 (15)0.37357 (12)0.0517 (5)
H130.02330.45730.37100.062*
C150.2886 (4)0.72672 (16)0.30428 (13)0.0581 (5)
H15A0.34450.77810.28090.087*
H15B0.37770.69650.33620.087*
H15C0.18630.74490.33610.087*
C140.0774 (3)0.71461 (16)0.18933 (14)0.0578 (5)
H14A0.13370.76660.16730.087*
H14B−0.02510.73190.22150.087*
H14C0.03470.67670.14790.087*
C160.1535 (2)0.41093 (12)0.11881 (10)0.0393 (4)
C170.2309 (3)0.34891 (14)0.16965 (10)0.0449 (4)
H170.27930.36770.21730.054*
C180.2366 (3)0.26016 (14)0.15030 (11)0.0443 (4)
H180.28890.21950.18480.053*
C190.1647 (2)0.23100 (12)0.07945 (10)0.0402 (4)
C200.0887 (3)0.29189 (13)0.02797 (11)0.0430 (4)
H200.04140.2731−0.01990.052*
C210.0838 (3)0.38045 (14)0.04814 (10)0.0431 (4)
H210.03220.42100.01340.052*
C220.7010 (4)0.34767 (19)0.49303 (17)0.0719 (7)
H22A0.73490.30450.53180.108*
H22B0.73580.40590.51070.108*
H22C0.76320.33460.44480.108*
C230.1004 (4)0.10995 (15)−0.00595 (14)0.0605 (6)
H23A0.11520.0466−0.00890.091*
H23B0.16380.1374−0.04900.091*
H23C−0.02830.1245−0.00850.091*
O10.5033 (3)0.68301 (12)0.16938 (12)0.0732 (5)
O2−0.2050 (2)0.48520 (14)0.15739 (11)0.0753 (5)
O30.5071 (3)0.34479 (11)0.48087 (10)0.0640 (4)
O40.1751 (2)0.14144 (9)0.06582 (8)0.0509 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0311 (6)0.0576 (9)0.0412 (7)0.0002 (7)0.0008 (6)−0.0093 (7)
C20.0358 (8)0.0543 (10)0.0348 (8)−0.0009 (8)0.0034 (7)−0.0084 (7)
C30.0446 (9)0.0519 (10)0.0393 (8)0.0004 (8)0.0037 (8)−0.0051 (8)
C40.0461 (10)0.0531 (11)0.0442 (9)−0.0003 (9)0.0077 (8)0.0035 (8)
C50.0432 (9)0.0573 (11)0.0387 (8)0.0012 (9)0.0088 (8)−0.0034 (8)
C60.0403 (8)0.0522 (10)0.0331 (8)0.0041 (8)−0.0015 (7)−0.0029 (7)
N70.0347 (8)0.0767 (12)0.0654 (11)−0.0027 (8)−0.0038 (8)−0.0179 (10)
C80.0390 (8)0.0525 (11)0.0323 (7)−0.0055 (8)0.0015 (7)−0.0049 (8)
C90.0401 (9)0.0592 (11)0.0389 (9)−0.0079 (9)0.0024 (7)0.0025 (9)
C100.0432 (9)0.0621 (12)0.0449 (10)−0.0046 (9)−0.0008 (9)−0.0002 (9)
C110.0600 (12)0.0453 (10)0.0400 (9)−0.0028 (9)0.0003 (9)−0.0036 (8)
C120.0600 (12)0.0569 (12)0.0516 (11)−0.0158 (10)0.0075 (10)0.0059 (10)
C130.0410 (9)0.0638 (13)0.0504 (10)−0.0121 (10)0.0056 (9)0.0009 (10)
C150.0579 (12)0.0581 (12)0.0582 (12)−0.0077 (10)0.0029 (11)−0.0143 (10)
C140.0607 (13)0.0600 (12)0.0527 (11)0.0116 (11)−0.0001 (11)−0.0026 (10)
C160.0356 (8)0.0494 (9)0.0329 (7)0.0046 (8)−0.0010 (7)−0.0024 (7)
C170.0425 (9)0.0604 (11)0.0319 (8)0.0043 (9)−0.0063 (7)−0.0014 (8)
C180.0390 (9)0.0555 (11)0.0383 (8)0.0070 (8)−0.0033 (7)0.0074 (8)
C190.0324 (8)0.0480 (9)0.0403 (8)0.0009 (7)0.0050 (7)0.0008 (7)
C200.0420 (9)0.0533 (10)0.0336 (8)0.0022 (8)−0.0047 (7)−0.0021 (8)
C210.0432 (9)0.0523 (10)0.0337 (8)0.0060 (8)−0.0065 (7)0.0020 (8)
C220.0729 (16)0.0707 (16)0.0723 (15)0.0205 (14)−0.0010 (14)0.0133 (13)
C230.0649 (13)0.0527 (12)0.0638 (13)−0.0002 (11)−0.0052 (12)−0.0134 (11)
O10.0684 (10)0.0652 (10)0.0858 (13)−0.0185 (9)0.0299 (10)−0.0047 (9)
O20.0420 (8)0.1026 (14)0.0812 (11)0.0025 (9)−0.0132 (8)−0.0327 (11)
O30.0740 (11)0.0592 (9)0.0589 (9)−0.0050 (9)−0.0057 (9)0.0118 (8)
O40.0543 (8)0.0467 (7)0.0516 (7)0.0036 (6)−0.0011 (7)0.0001 (6)

Geometric parameters (Å, °)

N1—N71.328 (2)C13—H130.93
N1—C21.472 (2)C15—H15A0.96
N1—C61.479 (2)C15—H15B0.96
C2—C81.524 (3)C15—H15C0.96
C2—C31.537 (3)C14—H14A0.96
C2—H20.98C14—H14B0.96
C3—C41.519 (3)C14—H14C0.96
C3—C151.532 (3)C16—C211.386 (2)
C3—C141.550 (3)C16—C171.393 (3)
C4—O11.204 (2)C17—C181.376 (3)
C4—C51.519 (3)C17—H170.93
C5—C61.539 (3)C18—C191.389 (3)
C5—H5A0.97C18—H180.93
C5—H5B0.97C19—O41.370 (2)
C6—C161.513 (3)C19—C201.384 (3)
C6—H60.98C20—C211.377 (3)
N7—O21.225 (2)C20—H200.93
C8—C91.387 (3)C21—H210.93
C8—C131.396 (3)C22—O31.423 (3)
C9—C101.385 (3)C22—H22A0.96
C9—H90.93C22—H22B0.96
C10—C111.380 (3)C22—H22C0.96
C10—H100.93C23—O41.421 (3)
C11—O31.367 (3)C23—H23A0.96
C11—C121.390 (3)C23—H23B0.96
C12—C131.372 (3)C23—H23C0.96
C12—H120.93
N7—N1—C2114.87 (16)C12—C13—H13118.9
N7—N1—C6121.28 (17)C8—C13—H13118.9
C2—N1—C6121.97 (14)C3—C15—H15A109.5
N1—C2—C8109.72 (15)C3—C15—H15B109.5
N1—C2—C3108.78 (15)H15A—C15—H15B109.5
C8—C2—C3118.74 (16)C3—C15—H15C109.5
N1—C2—H2106.3H15A—C15—H15C109.5
C8—C2—H2106.3H15B—C15—H15C109.5
C3—C2—H2106.3C3—C14—H14A109.5
C4—C3—C15113.24 (18)C3—C14—H14B109.5
C4—C3—C2109.81 (16)H14A—C14—H14B109.5
C15—C3—C2111.14 (16)C3—C14—H14C109.5
C4—C3—C14104.71 (16)H14A—C14—H14C109.5
C15—C3—C14108.22 (18)H14B—C14—H14C109.5
C2—C3—C14109.47 (17)C21—C16—C17117.90 (17)
O1—C4—C5121.09 (19)C21—C16—C6120.07 (16)
O1—C4—C3122.78 (19)C17—C16—C6122.00 (16)
C5—C4—C3116.13 (17)C18—C17—C16120.84 (17)
C4—C5—C6118.19 (17)C18—C17—H17119.6
C4—C5—H5A107.8C16—C17—H17119.6
C6—C5—H5A107.8C17—C18—C19120.29 (18)
C4—C5—H5B107.8C17—C18—H18119.9
C6—C5—H5B107.8C19—C18—H18119.9
H5A—C5—H5B107.1O4—C19—C20124.43 (17)
N1—C6—C16112.22 (16)O4—C19—C18115.98 (17)
N1—C6—C5110.23 (15)C20—C19—C18119.58 (18)
C16—C6—C5111.48 (16)C21—C20—C19119.48 (17)
N1—C6—H6107.6C21—C20—H20120.3
C16—C6—H6107.6C19—C20—H20120.3
C5—C6—H6107.6C20—C21—C16121.90 (17)
O2—N7—N1114.82 (19)C20—C21—H21119.1
C9—C8—C13116.69 (19)C16—C21—H21119.1
C9—C8—C2126.27 (18)O3—C22—H22A109.5
C13—C8—C2117.03 (17)O3—C22—H22B109.5
C10—C9—C8121.70 (19)H22A—C22—H22B109.5
C10—C9—H9119.2O3—C22—H22C109.5
C8—C9—H9119.2H22A—C22—H22C109.5
C11—C10—C9120.41 (19)H22B—C22—H22C109.5
C11—C10—H10119.8O4—C23—H23A109.5
C9—C10—H10119.8O4—C23—H23B109.5
O3—C11—C10125.5 (2)H23A—C23—H23B109.5
O3—C11—C12115.6 (2)O4—C23—H23C109.5
C10—C11—C12118.9 (2)H23A—C23—H23C109.5
C13—C12—C11120.0 (2)H23B—C23—H23C109.5
C13—C12—H12120.0C11—O3—C22118.20 (19)
C11—C12—H12120.0C19—O4—C23116.96 (16)
C12—C13—C8122.26 (19)
N7—N1—C2—C8110.4 (2)C3—C2—C8—C13164.11 (17)
C6—N1—C2—C8−85.0 (2)C13—C8—C9—C10−0.6 (3)
N7—N1—C2—C3−118.2 (2)C2—C8—C9—C10−179.66 (17)
C6—N1—C2—C346.4 (2)C8—C9—C10—C11−0.6 (3)
N1—C2—C3—C4−60.6 (2)C9—C10—C11—O3−177.43 (19)
C8—C2—C3—C465.7 (2)C9—C10—C11—C121.6 (3)
N1—C2—C3—C15173.29 (16)O3—C11—C12—C13177.69 (18)
C8—C2—C3—C15−60.3 (2)C10—C11—C12—C13−1.4 (3)
N1—C2—C3—C1453.80 (19)C11—C12—C13—C80.2 (3)
C8—C2—C3—C14−179.83 (16)C9—C8—C13—C120.8 (3)
C15—C3—C4—O1−26.9 (3)C2—C8—C13—C12179.92 (19)
C2—C3—C4—O1−151.7 (2)N1—C6—C16—C21122.51 (18)
C14—C3—C4—O190.8 (3)C5—C6—C16—C21−113.29 (19)
C15—C3—C4—C5153.57 (19)N1—C6—C16—C17−59.4 (2)
C2—C3—C4—C528.7 (2)C5—C6—C16—C1764.8 (2)
C14—C3—C4—C5−88.7 (2)C21—C16—C17—C18−0.4 (3)
O1—C4—C5—C6−158.8 (2)C6—C16—C17—C18−178.54 (18)
C3—C4—C5—C620.8 (3)C16—C17—C18—C19−0.1 (3)
N7—N1—C6—C16−69.4 (2)C17—C18—C19—O4−179.38 (18)
C2—N1—C6—C16127.05 (19)C17—C18—C19—C200.6 (3)
N7—N1—C6—C5165.7 (2)O4—C19—C20—C21179.33 (18)
C2—N1—C6—C52.1 (2)C18—C19—C20—C21−0.7 (3)
C4—C5—C6—N1−37.0 (2)C19—C20—C21—C160.2 (3)
C4—C5—C6—C16−162.27 (16)C17—C16—C21—C200.3 (3)
C2—N1—N7—O2170.12 (19)C6—C16—C21—C20178.52 (18)
C6—N1—N7—O25.4 (3)C10—C11—O3—C223.6 (3)
N1—C2—C8—C9109.0 (2)C12—C11—O3—C22−175.5 (2)
C3—C2—C8—C9−16.9 (3)C20—C19—O4—C23−0.7 (3)
N1—C2—C8—C13−70.0 (2)C18—C19—O4—C23179.28 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15C···Cg1i0.962.973.9108 (26)167
C23—H23C···Cg1ii0.962.863.7201 (27)149

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2805).

References

  • Bruker (2004). SAINT and APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Dimmock, J. R., Arora, V. K., Wonko, S. L., Hamon, N. W., Quail, J. W., Jia, Z., Warrington, R. C., Fang, W. D. & Lee, J. S. (1990). Drug Des. Deliv.6, 183–194. [PubMed]
  • Mutus, B., Wagner, J. D., Talpas, C. J., Dimmock, J. R., Phillips, O. A. & Reid, R. S. (1989). Anal. Biochem. pp. 237–243. [PubMed]
  • Nardelli, M. (1983). Acta Cryst. C39, 1141–1142.
  • Perumal, R. V., Agiraj, M. & Shanmugapandiyan, P. (2001). Indian Drugs, 38, 156–159.
  • Sheldrick, G. M. (2001). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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