2,4-Bis(o-tolyl)-3-azabicyclo[3.3.1]nonan-9-one

Article abstract of DOI:10.1107/S0108270100009318

The crystal structure of 2,4-bis(o-tolyl)-3-azabicyclo[3.3.1]-nonan-9-one shows that the bicyclic ring system adopts the chair-chair conformation. The phenyl rings are equatorially disposed with respect to the bicyclic ring. A slight deviation is seen from the chair conformation in the case of cyclohexane ring. A mixture of cyclohexanone, o-tolualdehyde and ethanol was added to a warm solution of ammonium acetate in absolute ethanol. Crystals of the ketone were separated out and were washed.

Full text of DOI:10.1107/S0108270100009318

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
2,4-Bis(o-tolyl)-3-azabicyclo[3.3.1]-
nonan-9-one
L. Vijayalakshmi,a V. Parthasarathi,a* M. Venkatrajb and
R. Jeyaramanb
aDepartment of Physics, Bharathidasan University, Tiruchirappalli 620 024, India,
and bDepartment of Chemistry, Bharathidasan University, Tiruchirappalli 620 024,
India
Correspondence e-mail: sarati@bdu.ernet.in
Figure 1
The molecular structure of (I) showing 50% probability displacement
ellipsoids. H atoms have been omitted for clarity.
Received 13 March 2000
Accepted 27 June 2000
The crystal structure of the title compound, C22H25NO,
con®rms 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.
Experimental
A mixture of cyclohexanone (0.1 mol), o-tolualdehyde (0.2 mol) and
absolute ethanol (75±100 ml) was added to a warm solution of
ammonium acetate (0.15±0.20 mol) in absolute ethanol (200±250 ml).
The mixture was gently warmed on a hot plate until the yellow colour
changed to orange. Dry ether (100 ml) was added to the reaction
mixture after cooling and the solution was kept for 5 d. Pale-yellow
crystals of the ketone separated out and were washed with ethanol±
ether and then recrystallized from benzene±petroleum ether (b.p.
333±353 K) [yield 35±40%, m.p. 490±491 K].
Comment
The bicyclic [3.3.1]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.
Crystal data
3
C22H25NO
Mr = 319.43
Dx = 1.211 Mg m
Cu Kꢁ radiation
Cell parameters from 25
re¯ections
Monoclinic, P21=a
Ê
a = 7.692 (3) A
ꢂ = 2±25ꢁ
ꢃ = 0.564 mm
T = 293 (2) K
Ê
b = 16.825 (3) A
1
Ê
c = 13.7247 (18) A
ꢀ = 99.428 (18)ꢁ
3
Ê
V = 1752.1 (8) A
Z = 4
Rectangular block, pale yellow
0.15 Â 0.12 Â 0.10 mm
Data collection
Rigaku AFC-7S diffractometer
!/2ꢂ scans
Rint = 0.030
ꢂmax = 70.08ꢁ
Absorption correction: scan
(North et al., 1968)
Tmin = 0.928, Tmax = 0.942
3578 measured re¯ections
3312 independent re¯ections
2380 re¯ections with I > 2ꢄ(I)
h = 0 ! 9
k = 0 ! 20
l = 16 ! 16
In the cyclohexane ring of (I), atoms C7 and C9 deviate
from the C8/C1/C5/C6 plane by
3 standard re¯ections
every 100 re¯ections
intensity decay: negligible
0.537 (4) and
Ê
0.720 (3) A, 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
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.064
wR(F2) = 0.206
S = 1.101
3312 re¯ections
222 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢄ2(Fo2) + (0.1042P)2
+ 0.6146P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max < 0.001
C9ÐC5ÐC4ÐC16
177.9 (2) and C10ÐC2ÐC1ÐC9
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.
Áꢅmax = 0.34 e A
3
Ê
3
Ê
0.43 e A
Áꢅmin
=
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.0067 (10)
ꢀ
1240 # 2000 International Union of Crystallography Printed in Great Britain ± all rights reserved
Acta Cryst. (2000). C56, 1240±1241

organic compounds
Table 1
Selected geometric parameters (A, ).
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ZORTEP (Zsolnai, 1997); software used to prepare material for
publication: SHELXL97.
ꢁ
Ê
N3ÐC4
N3ÐC2
1.461 (3)
1.465 (3)
O1ÐC9
1.221 (3)
LV thanks the UGC, India, for the award of an FIP
fellowship. Thanks are due to Professor J. Shashidaraprasad
and Dr M. A. Sridhar for making the National Data Collection
Facility at Mysore University, supported by the Department of
Science and Technology, available for data collection.
C4ÐN3ÐC2
O1ÐC9ÐC5
N3ÐC2ÐC10
113.1 (2)
124.2 (2)
111.1 (2)
N3ÐC2ÐC1
N3ÐC4ÐC16
N3ÐC4ÐC5
110.1 (2)
111.5 (2)
109.6 (2)
C4ÐN3ÐC2ÐC1
C1ÐC9ÐC5ÐC6
C1ÐC9ÐC5ÐC4
C2ÐN3ÐC4ÐC5
C9ÐC5ÐC4ÐN3
C9ÐC5ÐC4ÐC16
C6ÐC5ÐC4ÐC16
C5ÐC9ÐC1ÐC8
C5ÐC9ÐC1ÐC2
58.3 (2)
63.3 (3)
61.8 (3)
58.9 (3)
58.4 (2)
177.9 (2)
61.6 (3)
64.1 (3)
60.8 (3)
N3ÐC2ÐC1ÐC9
C10ÐC2ÐC1ÐC8
C9ÐC1ÐC8ÐC7
C2ÐC1ÐC8ÐC7
C1ÐC8ÐC7ÐC6
C8ÐC7ÐC6ÐC5
C9ÐC5ÐC6ÐC7
C4ÐC5ÐC6ÐC7
56.9 (2)
60.7 (3)
54.0 (3)
65.8 (3)
45.0 (3)
44.1 (3)
52.1 (3)
67.9 (3)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: VJ1106). Services for accessing these data are
described at the back of the journal.
References
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Ê
Ê
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È
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(Molecular Structure Corporation, 1994); cell re®nement: MSC/AFC
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ꢀ
Acta Cryst. (2000). C56, 1240±1241
L. Vijayalakshmi et al. C22H25NO 1241