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The crystal structure of the title compound, C22H25NO, confirms that the bicyclic ring system adopts the chair-chair conformation. The phenyl rings are equatorially disposed with respect to the bicyclic ring. There is a slight deviation from the chair conformation in the case of the cyclo­hexane ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009318/vj1106sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009318/vj1106Isup2.hkl
Contains datablock I

CCDC reference: 152616

Comment top

The bicyclic nonane ring can exist in chair-chair, chair-boat and boat-boat conformations. Among these, the chair-chair conformation is the most favourable. In the present study of the title compound, (I), the bicyclic ring system also adopts the chair-chair conformation. \sch

In the cyclohexane ring of (I), atoms C7 and C9 deviate from the C8/C1/C5/C6 plane by −0.537 (4) and 0.720 (3) Å, respectively, indicating a departure from the ideal chair conformation (Brown et al., 1965; Webb & Becker, 1967). The piperidine ring has near-ideal chair conformation. The phenyl rings are equatorially disposed with respect to the piperidine ring, with the torsion angles C9—C5—C4—C16 − 177.9 (2) and C10—C2—C1—C9 179.2 (2)°. They are oriented at an angle of 29.4 (1)° to each other. The orientations of the two o-tolyl groups are such that their methyl groups point towards the carbonyl group in the fused ring system.

Experimental top

A mixture of cyclohexanone (0.1 mole), the appropriate aldehydes (0.2 mole) and absolute ethanol (75–100 ml) was added to a warm solution of ammonium acetate (0.15–0.20 mole) in absolute ethanol (200–250 ml). The mixture was gently warmed on a hot plate till the yellow colour turned orange. Dry ether (100 ml) was added to the reaction mixture after cooling and the solution was kept for 1 to 20 d, depending on the aldehyde used. Pale-yellow crystals of the ketone separated out and were washed with ethanol-ether and then recrystallized from benzene-petroleum ether [yield 80%, m.p. 490 K]. Query specific aldehyde, No. of days and temp range for pet ether.

Refinement top

All H atoms were located from difference Fourier maps and their displacement parameters were refined in four groups. Details? Geometrical calculations were performed using PARST (Nardelli, 1996).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids. H atoms are omitted for clarity.
2,4-o-tolyl-3-azabicyclo[3.3.1]nonan-9-one top
Crystal data top
C22H25NOF(000) = 688
Mr = 319.43Dx = 1.211 Mg m3
Monoclinic, P21/aCu Kα radiation, λ = 1.54180 Å
a = 7.692 (3) ÅCell parameters from 25 reflections
b = 16.825 (3) Åθ = 2–25°
c = 13.7247 (18) ŵ = 0.56 mm1
β = 99.428 (18)°T = 293 K
V = 1752.1 (8) Å3Rectangular block, pale-yellow
Z = 40.15 × 0.12 × 0.10 mm
Data collection top
Rigaku AFC-7S
diffractometer
2380 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
Graphite monochromatorθmax = 70.1°, θmin = 3.3°
ω/2θ scansh = 09
Absorption correction: ψ-scan
(North et al., 1968)
k = 020
Tmin = 0.928, Tmax = 0.942l = 1616
3578 measured reflections3 standard reflections every 100 reflections
3312 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.206Calculated w = 1/[σ2(Fo2) + (0.1042P)2 + 0.6146P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
3312 reflectionsΔρmax = 0.34 e Å3
222 parametersΔρmin = 0.43 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0067 (10)
Crystal data top
C22H25NOV = 1752.1 (8) Å3
Mr = 319.43Z = 4
Monoclinic, P21/aCu Kα radiation
a = 7.692 (3) ŵ = 0.56 mm1
b = 16.825 (3) ÅT = 293 K
c = 13.7247 (18) Å0.15 × 0.12 × 0.10 mm
β = 99.428 (18)°
Data collection top
Rigaku AFC-7S
diffractometer
2380 reflections with I > 2σ(I)
Absorption correction: ψ-scan
(North et al., 1968)
Rint = 0.030
Tmin = 0.928, Tmax = 0.9423 standard reflections every 100 reflections
3578 measured reflections intensity decay: none
3312 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.206H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.34 e Å3
3312 reflectionsΔρmin = 0.43 e Å3
222 parameters
Special details top

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) top
xyzUiso*/Ueq
N30.1706 (2)0.53089 (12)0.67793 (14)0.0523 (5)
H30.05890.52880.67790.082 (2)*
O10.6712 (2)0.59560 (13)0.72250 (17)0.0768 (6)
C90.5137 (3)0.59620 (15)0.72622 (19)0.0564 (6)
C20.3010 (3)0.49294 (15)0.75338 (17)0.0523 (6)
H20.36800.45480.72020.082 (2)*
C50.3777 (3)0.63727 (15)0.65238 (18)0.0534 (6)
H50.43670.66190.60190.082 (2)*
C40.2498 (3)0.57258 (14)0.60271 (17)0.0503 (6)
H40.31830.53400.57110.082 (2)*
C10.4320 (3)0.55584 (16)0.80509 (19)0.0564 (6)
H10.52490.52850.85030.082 (2)*
C160.1110 (3)0.60799 (14)0.52393 (17)0.0504 (6)
C210.1460 (3)0.62139 (15)0.42837 (18)0.0544 (6)
C100.2125 (3)0.44759 (15)0.82667 (18)0.0532 (6)
C230.3139 (4)0.5945 (2)0.3952 (2)0.0734 (8)
H23A0.32740.53820.40490.129 (6)*
H23B0.41240.62140.43310.129 (6)*
H23C0.30880.60670.32640.129 (6)*
C200.0186 (4)0.65987 (16)0.36079 (19)0.0613 (7)
H200.04100.66910.29720.082 (2)*
C110.2944 (4)0.38124 (16)0.87707 (19)0.0593 (6)
C170.0509 (3)0.63142 (17)0.54732 (19)0.0595 (6)
H170.07680.62130.61000.082 (2)*
C150.0473 (3)0.47114 (17)0.8455 (2)0.0615 (7)
H150.00870.51440.81170.082 (2)*
C120.2083 (5)0.34299 (19)0.9449 (2)0.0756 (8)
H120.26210.29950.97910.082 (2)*
C190.1385 (4)0.68458 (17)0.3851 (2)0.0679 (7)
H190.22030.71110.33900.082 (2)*
C180.1739 (4)0.66980 (18)0.4779 (2)0.0697 (8)
H180.28110.68560.49450.082 (2)*
C140.0345 (4)0.4313 (2)0.9133 (2)0.0744 (8)
H140.14450.44800.92510.082 (2)*
C220.4696 (4)0.35003 (19)0.8588 (2)0.0759 (8)
H22A0.46480.34040.78950.129 (6)*
H22B0.49610.30130.89460.129 (6)*
H22C0.55980.38850.88070.129 (6)*
C130.0456 (5)0.3673 (2)0.9632 (2)0.0818 (9)
H130.00910.34051.00920.082 (2)*
C80.3509 (4)0.62076 (17)0.86298 (19)0.0638 (7)
H8A0.28930.59540.91090.082 (2)*
H8B0.44530.65250.89910.082 (2)*
C70.2235 (4)0.67548 (16)0.7987 (2)0.0629 (7)
H7A0.20070.72160.83720.082 (2)*
H7B0.11260.64790.77900.082 (2)*
C60.2925 (4)0.70325 (15)0.7066 (2)0.0592 (6)
H6A0.37880.74490.72510.082 (2)*
H6B0.19560.72620.66120.082 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N30.0457 (10)0.0580 (12)0.0532 (11)0.0026 (8)0.0085 (8)0.0034 (9)
O10.0429 (10)0.0894 (15)0.1002 (16)0.0011 (9)0.0182 (9)0.0108 (12)
C90.0488 (13)0.0553 (14)0.0655 (15)0.0024 (10)0.0106 (11)0.0039 (11)
C20.0498 (12)0.0548 (13)0.0526 (13)0.0015 (10)0.0100 (10)0.0012 (10)
C50.0488 (13)0.0557 (14)0.0569 (13)0.0062 (10)0.0126 (10)0.0034 (11)
C40.0511 (13)0.0513 (13)0.0502 (12)0.0006 (10)0.0130 (10)0.0027 (10)
C10.0463 (13)0.0626 (15)0.0586 (14)0.0044 (11)0.0034 (10)0.0044 (11)
C160.0506 (13)0.0499 (12)0.0516 (12)0.0010 (10)0.0110 (10)0.0050 (10)
C210.0602 (14)0.0521 (13)0.0517 (13)0.0054 (11)0.0119 (11)0.0070 (10)
C100.0546 (13)0.0548 (13)0.0502 (12)0.0069 (10)0.0086 (10)0.0028 (10)
C230.0703 (18)0.093 (2)0.0619 (16)0.0036 (15)0.0266 (14)0.0042 (15)
C200.0755 (17)0.0573 (14)0.0490 (13)0.0064 (12)0.0034 (12)0.0014 (11)
C110.0617 (15)0.0581 (14)0.0555 (14)0.0072 (11)0.0017 (11)0.0041 (11)
C170.0517 (13)0.0695 (16)0.0578 (14)0.0023 (12)0.0111 (11)0.0053 (12)
C150.0581 (15)0.0650 (15)0.0640 (15)0.0056 (12)0.0179 (12)0.0045 (12)
C120.091 (2)0.0690 (18)0.0648 (16)0.0162 (16)0.0062 (15)0.0107 (14)
C190.0682 (17)0.0638 (16)0.0655 (16)0.0047 (13)0.0073 (13)0.0034 (13)
C180.0558 (15)0.0774 (18)0.0731 (18)0.0074 (13)0.0022 (13)0.0098 (15)
C140.0740 (19)0.080 (2)0.0750 (19)0.0190 (15)0.0290 (15)0.0114 (16)
C220.0687 (18)0.0756 (19)0.080 (2)0.0083 (15)0.0020 (15)0.0155 (16)
C130.093 (2)0.086 (2)0.0718 (18)0.0297 (18)0.0297 (17)0.0039 (17)
C80.0666 (16)0.0692 (17)0.0542 (14)0.0110 (13)0.0056 (12)0.0071 (12)
C70.0651 (15)0.0608 (15)0.0644 (15)0.0010 (12)0.0148 (12)0.0134 (12)
C60.0579 (14)0.0521 (13)0.0665 (15)0.0011 (11)0.0075 (12)0.0040 (12)
Geometric parameters (Å, º) top
N3—C41.461 (3)C20—H200.9300
N3—C21.465 (3)C11—C121.386 (4)
N3—H30.8600C11—C221.506 (4)
O1—C91.221 (3)C17—C181.387 (4)
C9—C11.500 (3)C17—H170.9300
C9—C51.501 (3)C15—C141.380 (4)
C2—C101.511 (3)C15—H150.9300
C2—C11.551 (3)C12—C131.379 (5)
C2—H20.9800C12—H120.9300
C5—C61.541 (3)C19—C181.368 (4)
C5—C41.548 (3)C19—H190.9300
C5—H50.9800C18—H180.9300
C4—C161.512 (3)C14—C131.367 (5)
C4—H40.9800C14—H140.9300
C1—C81.542 (4)C22—H22A0.9600
C1—H10.9800C22—H22B0.9600
C16—C171.393 (3)C22—H22C0.9600
C16—C211.400 (3)C13—H130.9300
C21—C201.393 (4)C8—C71.517 (4)
C21—C231.508 (4)C8—H8A0.9700
C10—C151.395 (4)C8—H8B0.9700
C10—C111.407 (4)C7—C61.523 (4)
C23—H23A0.9600C7—H7A0.9700
C23—H23B0.9600C7—H7B0.9700
C23—H23C0.9600C6—H6A0.9700
C20—C191.370 (4)C6—H6B0.9700
C4—N3—C2113.08 (18)C12—C11—C10118.3 (3)
C4—N3—H3123.5C12—C11—C22119.3 (3)
C2—N3—H3123.5C10—C11—C22122.4 (2)
O1—C9—C1124.2 (2)C18—C17—C16120.5 (3)
O1—C9—C5124.2 (2)C18—C17—H17119.7
C1—C9—C5111.6 (2)C16—C17—H17119.7
N3—C2—C10111.08 (19)C14—C15—C10121.1 (3)
N3—C2—C1110.1 (2)C14—C15—H15119.4
C10—C2—C1111.72 (19)C10—C15—H15119.4
N3—C2—H2107.9C13—C12—C11122.2 (3)
C10—C2—H2107.9C13—C12—H12118.9
C1—C2—H2107.9C11—C12—H12118.9
C9—C5—C6108.1 (2)C18—C19—C20119.3 (3)
C9—C5—C4107.2 (2)C18—C19—H19120.3
C6—C5—C4115.4 (2)C20—C19—H19120.3
C9—C5—H5108.6C19—C18—C17120.5 (3)
C6—C5—H5108.6C19—C18—H18119.8
C4—C5—H5108.6C17—C18—H18119.8
N3—C4—C16111.51 (19)C13—C14—C15120.2 (3)
N3—C4—C5109.55 (19)C13—C14—H14119.9
C16—C4—C5111.17 (19)C15—C14—H14119.9
N3—C4—H4108.2C11—C22—H22A109.5
C16—C4—H4108.2C11—C22—H22B109.5
C5—C4—H4108.2H22A—C22—H22B109.5
C9—C1—C8107.7 (2)C11—C22—H22C109.5
C9—C1—C2107.2 (2)H22A—C22—H22C109.5
C8—C1—C2115.6 (2)H22B—C22—H22C109.5
C9—C1—H1108.7C14—C13—C12119.4 (3)
C8—C1—H1108.7C14—C13—H13120.3
C2—C1—H1108.7C12—C13—H13120.3
C17—C16—C21119.1 (2)C7—C8—C1114.1 (2)
C17—C16—C4120.0 (2)C7—C8—H8A108.7
C21—C16—C4120.8 (2)C1—C8—H8A108.7
C20—C21—C16118.5 (2)C7—C8—H8B108.7
C20—C21—C23118.8 (2)C1—C8—H8B108.7
C16—C21—C23122.7 (2)H8A—C8—H8B107.6
C15—C10—C11118.9 (2)C8—C7—C6112.9 (2)
C15—C10—C2120.2 (2)C8—C7—H7A109.0
C11—C10—C2120.9 (2)C6—C7—H7A109.0
C21—C23—H23A109.5C8—C7—H7B109.0
C21—C23—H23B109.5C6—C7—H7B109.0
H23A—C23—H23B109.5H7A—C7—H7B107.8
C21—C23—H23C109.5C7—C6—C5114.4 (2)
H23A—C23—H23C109.5C7—C6—H6A108.7
H23B—C23—H23C109.5C5—C6—H6A108.7
C19—C20—C21122.1 (3)C7—C6—H6B108.7
C19—C20—H20119.0C5—C6—H6B108.7
C21—C20—H20119.0H6A—C6—H6B107.6
C4—N3—C2—C10177.41 (19)N3—C2—C10—C1527.8 (3)
C4—N3—C2—C158.3 (2)C1—C2—C10—C1595.6 (3)
O1—C9—C5—C6116.8 (3)N3—C2—C10—C11152.2 (2)
C1—C9—C5—C663.3 (3)C1—C2—C10—C1184.3 (3)
O1—C9—C5—C4118.1 (3)C16—C21—C20—C190.1 (4)
C1—C9—C5—C461.8 (3)C23—C21—C20—C19178.7 (3)
C2—N3—C4—C16177.62 (19)C15—C10—C11—C121.2 (4)
C2—N3—C4—C558.9 (3)C2—C10—C11—C12178.7 (2)
C9—C5—C4—N358.4 (2)C15—C10—C11—C22177.9 (3)
C6—C5—C4—N362.1 (3)C2—C10—C11—C222.2 (4)
C9—C5—C4—C16177.90 (19)C21—C16—C17—C182.0 (4)
C6—C5—C4—C1661.6 (3)C4—C16—C17—C18174.8 (2)
O1—C9—C1—C8116.0 (3)C11—C10—C15—C141.0 (4)
C5—C9—C1—C864.1 (3)C2—C10—C15—C14178.9 (2)
O1—C9—C1—C2119.0 (3)C10—C11—C12—C130.8 (4)
C5—C9—C1—C260.8 (3)C22—C11—C12—C13178.4 (3)
N3—C2—C1—C956.9 (2)C21—C20—C19—C181.3 (4)
C10—C2—C1—C9179.2 (2)C20—C19—C18—C171.1 (4)
N3—C2—C1—C863.2 (3)C16—C17—C18—C190.6 (4)
C10—C2—C1—C860.7 (3)C10—C15—C14—C130.3 (4)
N3—C4—C16—C1729.3 (3)C15—C14—C13—C120.2 (5)
C5—C4—C16—C1793.3 (3)C11—C12—C13—C140.0 (5)
N3—C4—C16—C21154.0 (2)C9—C1—C8—C754.0 (3)
C5—C4—C16—C2183.5 (3)C2—C1—C8—C765.8 (3)
C17—C16—C21—C201.8 (4)C1—C8—C7—C645.0 (3)
C4—C16—C21—C20175.0 (2)C8—C7—C6—C544.1 (3)
C17—C16—C21—C23177.0 (2)C9—C5—C6—C752.1 (3)
C4—C16—C21—C236.3 (4)C4—C5—C6—C767.9 (3)

Experimental details

Crystal data
Chemical formulaC22H25NO
Mr319.43
Crystal system, space groupMonoclinic, P21/a
Temperature (K)293
a, b, c (Å)7.692 (3), 16.825 (3), 13.7247 (18)
β (°) 99.428 (18)
V3)1752.1 (8)
Z4
Radiation typeCu Kα
µ (mm1)0.56
Crystal size (mm)0.15 × 0.12 × 0.10
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correctionψ-scan
(North et al., 1968)
Tmin, Tmax0.928, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections
3578, 3312, 2380
Rint0.030
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.206, 1.10
No. of reflections3312
No. of parameters222
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.43

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
N3—C41.461 (3)O1—C91.221 (3)
N3—C21.465 (3)
C4—N3—C2113.08 (18)N3—C2—C1110.1 (2)
O1—C9—C5124.2 (2)N3—C4—C16111.51 (19)
N3—C2—C10111.08 (19)N3—C4—C5109.55 (19)
C4—N3—C2—C158.3 (2)N3—C2—C1—C956.9 (2)
C1—C9—C5—C663.3 (3)C10—C2—C1—C860.7 (3)
C1—C9—C5—C461.8 (3)C9—C1—C8—C754.0 (3)
C2—N3—C4—C558.9 (3)C2—C1—C8—C765.8 (3)
C9—C5—C4—N358.4 (2)C1—C8—C7—C645.0 (3)
C9—C5—C4—C16177.90 (19)C8—C7—C6—C544.1 (3)
C6—C5—C4—C1661.6 (3)C9—C5—C6—C752.1 (3)
C5—C9—C1—C864.1 (3)C4—C5—C6—C767.9 (3)
C5—C9—C1—C260.8 (3)
 

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