6-(1-Hydroxy-2,2-diphenylethyl)-4,4-diphenyl-2-cyclohexen-1-one

Article abstract of DOI:10.1107/S010827019901553X

The crystal structure of the title compound, C₃₂H₂₈O₂, (I), confirms the erythro stereochemistry of the aldol adduct. In the crystal, (I) forms centrosymmetric O-H...O=C hydrogen-bonded dimers which in turn are connected by C-H...O and C-H...π interactions.

Full text of DOI:10.1107/S010827019901553X

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
6-(1-Hydroxy-2,2-diphenylethyl)-4,4-
diphenyl-2-cyclohexen-1-one
V. S. Senthil Kumar and Ashwini Nangia*
School of Chemistry, University of Hyderabad, Hyderabad 500 046, India
Correspondence e-mail: ansc@uohyd.ernet.in
Received 22 October 1999
Accepted 29 November 1999
The crystal structure of the title compound, C32H28O2, (I),
con®rms the erythro stereochemistry of the aldol adduct. In
the crystal, (I) forms centrosymmetric OÐHÁ Á ÁO C
hydrogen-bonded dimers which in turn are connected by
Figure 1
ORTEPII (Johnson, 1976) diagram and atom-numbering scheme for (I);
displacement ellipsoids are drawn at the 50% probability level for non-H
atoms.
CÐHÁ Á ÁO and CÐHÁ Á Áꢀ interactions.
ꢁ
Ê
2.73 A, 170.0 ). The chains are interlinked by Cphenyl
Ð
Comment
HÁ Á ÁOhydroxyl interactions along [010] (C16ÐH16AÁ Á ÁO2
ꢁ
Ê
2.51 A, 132.5 ), not shown in Fig. 2.
During studies of the crystal structure of 4,4-diphenyl-2,5-
cyclohexadien-1-one (Anthony et al., 1998), the title
compound, (I), was obtained as a by-product in the base-
catalysed condensation of diphenylacetaldehyde with methyl
vinyl ketone (Zimmerman et al., 1968) (see scheme). The
chemical structure is consistent with (I) based on its NMR and
IR spectra. The stereochemistry of (I) was established by
X-ray diffraction and con®rmed to be erythro at C2 and C19
stereogenic centres. The ready reversibility of aldol conden-
sation under the equilibrium conditions of alcoholic KOH
medium provides the expected erythro diastereomer (House,
1972). The molecular geometry of (I) in the crystal is shown in
Fig. 1 (Johnson, 1976).
Allen et al. (1999) have reported on the probabilities of
formation of cyclic hydrogen-bond intermolecular motifs in
organic crystal structures archived in the Cambridge Struc-
tural Database. Supramolecular synthon (II) occurs in
20 structures out of a possible 282 molecules that contain the
ꢁ-hydroxy carbonyl functional group, giving it a probability of
formation (Ps) of 0.07. While the Ps of motif (II) is low and its
overall ranking 71/75 in the CSD analysis, it may be noted that
the occurrence of this synthon is more frequent in crystal
structures of aldol adducts (Fair et al., 1985; Gleiter et al., 1996;
Gross & Finn, 1994; Lodge & Heathcock, 1987).
In the crystal, inversion-related molecules of (I) form OÐ
HÁ Á ÁO C dimers, (II), in the (110) layer between the hydroxy
Ê
group and the carbonyl-O atom [O2ÐH2AÁ Á ÁO1 1.90 (2) A,
176.6 (15)ꢁ] (Fig. 2). Such dimers are in turn connected by CÐ
HÁ Á ÁO and CÐHÁ Á Áꢀ interactions (Desiraju & Steiner, 1999)
along [100] from the phenyl- and ole®n-H atoms to the
carbonyl and phenyl (C21±C26) acceptor groups, respectively
Figure 2
View of (I) in [101] showing the centrosymmetric OÐHÁ Á ÁO dimer, (II),
(C29ÐH29AÁ Á ÁO1 2.59 A, 161.4ꢁ; C5ÐH5AÁ Á Áꢀcentroid
and the intermolecular CÐHÁ Á ÁO and CÐHÁ Á Áꢀ interactions.
Ê
ꢀ
360 # 2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved

organic compounds
Data collection: SMART (Siemens, 1996); cell re®nement: SAINT
(Siemens, 1996); data reduction: SHELXTL (Siemens, 1994);
program(s) used to solve structure: SHELXS97 (Sheldrick, 1990);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEPII (Johnson, 1976) and PLUTON (Spek,
1992); software used to prepare material for publication:
SHELXL97.
Experimental
Compound (I) was synthesized as shown in the scheme (Zimmerman
et al., 1968). Crystals were obtained upon recrystallization from 5%
ethyl acetate/hexane (m.p. 457 K).
Crystal data
C32H28O2
Z = 2
Dx = 1.228 Mg m
Mo Kꢂ radiation
3
Mr = 444.54
Triclinic, P1
a = 9.6111 (9) A
b = 11.5199 (12) A
c = 11.5621 (12) A
Ê
Cell parameters from 1500
re¯ections
We thank Professor W. T. Robinson and Dr R. Kadirvelraj
(University of Canterbury, New Zealand) for X-ray data
collection. VSSK thanks the CSIR (1/1431/96/EMR-II) for
fellowship support. We thank Professor G. R. Desiraju for
helpful discussion.
Ê
Ê
ꢄ = 1.9±21.5ꢁ
ꢅ = 0.075 mm
T = 168 (2) K
1
ꢂ = 84.458 (1)ꢁ
ꢁ = 77.829 (1)ꢁ
ꢃ = 74.138 (1)ꢁ
Prism, colourless
0.5 Â 0.31 Â 0.15 mm
3
Ê
V = 1202.7 (2) A
Data collection
CCD area-detector diffractometer
' and ! scans
10624 measured re¯ections
4605 independent re¯ections
3460 re¯ections with I > 2ꢆ(I)
Rint = 0.016
ꢄ
max = 26.37ꢁ
h = 5 ! 11
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: JZ1380). Services for accessing these data are
described at the back of the journal.
k = 14 ! 14
l = 13 ! 14
Intensity decay: none
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.035
wR(F2) = 0.093
S = 1.051
4605 re¯ections
337 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
References
Allen, F. H., Motherwell, W. D. S., Raithby, P. R., Shields, G. P. & Taylor, R.
(1999). New J. Chem. 23, 25±34.
Anthony, A., Desiraju, G. R., Jetti, R. K. R., Kuduva, S. S., Madhavi, N. N. L.,
Nangia, A., Thaimattam, R. & Thalladi, V. R. (1998). Cryst. Eng. 1, 1±18.
Desiraju, G. R. & Steiner, T. (1999). In The Weak Hydrogen Bond in Structural
Chemistry and Biology. Oxford University Press.
Fair, C. K., Clark, G. R. & Nikaido, M. M. (1985). Acta Cryst. C41, 155±157.
Gleiter, R., Ackermann, U., Oeser, T. & Irngartinger, H. (1996). Chem. Eur. J.
2, 271±277.
Gross, M. F. & Finn, M. G. (1994). J. Am. Chem. Soc. 116, 10921±10933.
House, H. O. (1972). Modern Synthetic Reactions, 2nd ed., pp. 630±631.
California: The Benjamin/Cummings Publishing Company.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
w = 1/[ꢆ2(Fo2) + (0.0549P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max = 0.001
3
Ê
Áꢇmax = 0.17 e A
3
Ê
0.18 e A
Áꢇmin
=
Table 1
Hydrogen-bonding geometry (A, ).
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O2ÐH2AÁ Á ÁO1i
C16ÐH16AÁ Á ÁO2ii
C29ÐH29AÁ Á ÁO1iii
C5ÐH5AÁ Á Áꢀiv
0.914 (18)
0.95
0.95
1.903 (18)
2.51
2.59
2.8163 (14)
3.2325 (19)
3.512 (2)
3.67
176.6 (15)
133
161
Lodge, E. P. & Heathcock, C. H. (1987). J. Am. Chem. Soc. 109, 3353±3361.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473.
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Siemens (1994). SHELXTL. Release 5.03. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
0.95
2.73
170
È
Symmetry codes: (i) x; 2 y; z; (ii) x; 1 y; z; (iii)
1; y; z.
1
x; 2 y; z; (iv)
x
Siemens (1996). SMART and SAINT. Version 4.050. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
Spek, A. L. (1992). PLUTON. University of Utrecht, The Netherlands.
Zimmerman, H. E., Hancock, K. G. & Licke, G. C. (1968). J. Am. Chem. Soc.
90, 4892±4911.
The hydroxyl-H atom was identi®ed from a Fourier synthesis and
re®ned freely. H atoms bonded to carbon were generated at idealized
geometries and re®ned isotropically using a riding model.
ꢀ
Acta Cryst. (2000). C56, 360±361
Senthil Kumar and Nangia C32H28O2 361