9,10-diphenyl-9,10-epidioxyanthracene and 9,10-dihydro-10,10-dimethoxy-9-phenylanthracen-9-ol

Article abstract of DOI:10.1107/S0108270103007625

9,10-Diphenyl-9,10-epidioxyanthracene, C₂₆H₁₈O₂, (I), was accidentally used in a photooxygenation reaction that produced 9,10-dihydro-10,10-dimethoxy-9-phenylanthracen-9-ol, C₂₂H₂₀O₃, (II).

Full text of DOI:10.1107/S0108270103007625

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
with the aim of inducing singlet oxygen reactions, and
obtained (II), a phenylanthracene derivative, as one of the
products. We have structurally analyzed both (I) and (II), and
the results are presented here.
ISSN 0108-2701
The asymmetric unit of (I) consists of two crystal-
lographically independent molecules, viz. A and B, related by
a local pseudo-twofold rotation axis. The bond lengths and
angles of molecules A and B (Fig. 1 and Table 1) agree with
each other and are within normal ranges (Allen et al., 1987).
In both molecules, within the C1±C14 anthracene moiety,
the C1ÐC6ÐC7ÐC8ÐC13ÐC14 ring exhibits a boat
conformation, with atoms C7 and C14 displaced by 0.627 (4)
9
,10-Diphenyl-9,10-epidioxy-
anthracene and 9,10-dihydro-
0,10-dimethoxy-9-phenylanthra-
cen-9-ol
1
Ê
and 0.644 (4) A, respectively, from the C1/C6/C8/C13 plane in
molecule A; the corresponding displacements in molecule B
a
a
b
Anwar Usman, Hoong-Kun Fun, * Yun Li and
b
Jian-Hua Xu
Ê
are 0.659 (4) and 0.644 (4) A. The two fused benzene rings,
a
C1±C6 and C8±C13, make dihedral angles with the C1/C6/C8/
ꢀ
X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia,
b
C13 plane of 21.8 (2) and 19.5 (2) in molecule A, and 26.1 (2)
ꢀ
1
1800 USM, Penang, Malaysia, and Department of Chemistry, Nanjing
University, Nanjing 210093, People's Republic of China
Correspondence e-mail: hkfun@usm.my
and 23.4 (2) in molecule B. The C1/C6/C8/C13 plane is
orthogonal to the C7/O2/O1/C14 plane, with the dihedral
ꢀ
angle between the two planes being 89.7 (2) and 89.9 (2) in
molecules A and B, respectively.
Received 24 March 2003
Accepted 4 April 2003
Online 10 May 2003
9
,10-Diphenyl-9,10-epidioxyanthracene, C H O , (I), was
26 18 2
accidentally used in a photooxygenation reaction that
produced 9,10-dihydro-10,10-dimethoxy-9-phenylanthracen-
9
-ol, C H O , (II). In both compounds, the phenyl rings
22 20 3
are approximately orthogonal to the anthracene moiety. The
conformation of the anthracene moiety differs as a result of
substitution. Intramolecular CÐHÁ Á ÁO interactions in (I)
form two approximately planar S(5) rings in each of the two
crystallographically independent molecules. The packing of (I)
and (II) consists of molecular dimers stabilized by CÐHÁ Á ÁO
interactions and of molecular chains stabilized by OÐHÁ Á ÁO
interactions, respectively.
Comment
Figure 1
Aview of the structure of (I), showing displacement ellipsoids at the 50%
probability level and the atom-numbering scheme. All H atoms have
been omitted for clarity.
9
,10-Diphenylanthracene endoperoxide, (I), is a well known
chemical source that releases singlet oxygen when heated in
benzene and other solvents (Wasserman & Scheffer, 1967).
During the course of our investigation of the singlet oxygen
The C7/O2/O1/C14 plane is approximately coplanar with
the C15±C20 and C21±C26 phenyl rings, with the dihedral
angles between the plane and the rings being 5.3 (2) and
ꢀ
ꢀ
2
.3 (2) in molecule A, and 4.6 (2) and 1.6 (1) in molecule B.
This coplanarity is maintained by intramolecular C16Ð
H16Á Á ÁO1 and C26ÐH26Á Á ÁO2 interactions, which form O1Ð
C14ÐC15ÐC16ÐH16 and O2ÐC7ÐC21ÐC26ÐH26 S(5)
rings (Etter et al., 1990) in both molecules (Fig. 1 and Table 2).
The dihedral angles differ between molecules A and B
because atom O1 in molecule A facilitates an intermolecular
i
C17BÐH17BÁ Á ÁO1A interaction (see Table 2 for geometric
reactions of indolizine derivatives (Tian et al., 2001), we
re¯uxed (I) with an indolizine sample in toluene±methanol,
parameters and symmetry code), which connects molecules A
and B from different asymmetric units into dimers.
o308 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103007625
Acta Cryst. (2003). C59, o308±o310

organic compounds
molecular chains along the b direction (Fig. 3), stabilized by
ii
O1ÐH1O1Á Á ÁO3 interactions (see Table 3 for geometric
parameters and symmetry code).
Experimental
Compound (I) was prepared by methylene blue-sensitized photo-
oxygenation of 9,10-diphenylanthracene and was separated by
column chromatography on silica gel with petroleum ether and ethyl
acetate eluants. Compound (II) was obtained accidentally by
re¯uxing a toluene±methanol solution of 1-(4-methoxybenzoyl)-2-
phenylindolizine with (I). Compound (II) was also separated by
column chromatography on silica gel with petroleum ether and ethyl
acetate as eluants. Single crystals of (I) and (II) were obtained by
slow evaporation of their petroleum ether/ethyl acetate solutions.
Figure 2
A view of the structure of (II), showing displacement ellipsoids at the
Compound (I)
50% probability level and the atom-numbering scheme. All H atoms have
been omitted for clarity.
Crystal data
C
26
H O
18 2
Mo Kꢁ radiation
Cell parameters from 3581
re¯ections
r
M = 362.40
Monoclinic, P2 =c
1
Ê
a = 19.8390 (12) A
ꢀ
ꢂ = 2.3±28.3
ꢃ = 0.08 mm
T = 293 (2) K
In contrast to (I), the anthracene moiety of (II) is planar to
Ê
Ê
b = 10.4950 (6) A
� 1
within Æ0.042 (3) A (Fig 2). An intramolecular C16Ð
Ê
c = 18.0130 (10) A
ꢀ
H16Á Á ÁO1 interaction (Table 3), similar to the intramolecular
interactions in (I), forms an O1ÐC14ÐC15ÐC16ÐH16 S(5)
ring. This ring deviates slightly from planarity, having an O1Ð
ꢀ = 95.0160 (10)
Ê
V = 3736.1 (4) A
Z = 8
Cylinder, colorless
0.46 Â 0.20 Â 0.16 mm
3
� 3
D
x
= 1.289 Mg m
ꢀ
C14ÐC15ÐC16 torsion angle of 21.8 (3) . In (II), the two
Data collection
methoxy groups attached to atom C7 are coplanar. Both the
C21/O2/C7/O3/C22 plane and the C15±C20 phenyl ring are
orthogonal to the anthracene moiety, with dihedral angles of
Siemens SMART CCD area-
detector diffractometer
! scans
Rint = 0.069
ꢀ
ꢂ
max = 25.0
h = � 20 ! 23
k = � 12 ! 12
l = � 18 ! 21
ꢀ
1
6
3
8 226 measured re¯ections
575 independent re¯ections
917 re¯ections with I > 2ꢄ(I)
8
9.8 (2) and 81.3 (1) , respectively. The packing comprises
Re®nement
2
2
2
2
Re®nement on F
2
w = 1/[ꢄ (F ) + (0.0783P)
o
2
R[F > 2ꢄ(F )] = 0.091
wR(F ) = 0.218
S = 1.06
+ 6.3806P]
where P = (F + 2F )/3
o c
2
2
2
(Á/ꢄ)max < 0.001
Ê
� 3
Áꢅmax = 0.28 e A
6
5
575 re¯ections
05 parameters
Áꢅmin = � 0.35 e AÊ
� 3
H-atom parameters constrained
Table 1
Selected intramolecular distances (A) for (I).
Ê
O1AÐC14A
O1AÐO2A
O2AÐC7A
1.476 (5)
1.485 (4)
1.477 (5)
O1BÐC14B
O1BÐO2B
O2BÐC7B
1.478 (5)
1.483 (4)
1.471 (5)
Table 2
Hydrogen-bonding geometry (A, ) for (I).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C16AÐH16AÁ Á ÁO1A
C16BÐH16BÁ Á ÁO1B
0.93
0.93
0.93
0.93
0.93
2.31
2.30
2.58
2.33
2.29
2.678 (5)
2.667 (6)
3.299 (6)
2.689 (7)
2.666 (6)
103
103
134
102
103
i
C17BÐH17BÁ Á ÁO1A
C26AÐH26AÁ Á ÁO2A
C26BÐH26BÁ Á ÁO2B
Figure 3
Packing diagram of (II), showing chains parallel to the b direction. All H
atoms attached to C atoms have been omitted for clarity. Dashed lines
denote intermolecular OÐHÁ Á ÁO interactions.
3
2
1
2
Symmetry code: (i) x; � y; ‡ z.
ꢁ
Acta Cryst. (2003). C59, o308±o310
Anwar Usman et al.
C H
26 18
O
2
and C22
H
O
20 3
o309

organic compounds
Compound (II)
The H atoms of (I) were ®xed geometrically and treated as riding
Ê
on their parent C atoms, with CÐH distances of 0.96 A and Uiso(H)
Crystal data
values of 1.5Ueq(C). For (II), the H atoms attached to atoms C21 and
C22 were ®xed geometrically and treated as riding atoms, with CÐH
Ê
distances of 0.93 A and Uiso(H) values of 1.2Ueq(C). The remaining H
atoms were located in difference maps and were re®ned isotropically
�
3
C
H
22 20
O
3
D
x
= 1.283 Mg m
M
r
= 332.38
Mo Kꢁ radiation
Cell parameters from 3446
re¯ections
Monoclinic, P2 =c
1
Ê
a = 8.9181 (10) A
b = 11.3071 (12) A
Ê
ꢀ
Ê
[CÐH = 0.91 (3)±0.99 (2) A]. A rotating group re®nement was used
ꢂ = 2.9±28.3
ꢃ = 0.08 mm
T = 293 (2) K
Ê
c = 17.0624 (19) A
� 1
for the methyl groups. Owing to the large number of weak data at
ꢀ
ꢀ
ꢀ
= 90.552 (2)
higher angles, the maximum 2ꢂ value was limited to 50 for both (I)
and (II).
Ê
3
V = 1720.5 (3) A
Z = 4
Slab, colorless
0.36 Â 0.26 Â 0.20 mm
For both compounds, data collection: SMART (Siemens, 1996);
cell re®nement: SAINT (Siemens, 1996); data reduction: SAINT and
SADABS (Sheldrick, 1996); program(s) used to solve structure:
SHELXTL (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXTL; molecular graphics: SHELXTL; software used to
prepare material for publication: SHELXTL, PARST (Nardelli,
Data collection
Siemens SMART CCD area-
detector diffractometer
3015 independent re¯ections
2366 re¯ections with I > 2ꢄ(I)
!
scans
Absorption correction: empirical
SADABS; Sheldrick, 1996)
min = 0.970, Tmax = 0.983
361 measured re¯ections
Rint = 0.024
ꢀ
ꢂ
max = 25.0
(
T
h = � 10 ! 10
k = � 13 ! 13
l = � 13 ! 20
1995) and PLATON (Spek, 2003).
8
The authors would like to thank the Malaysian Government
and Universiti Sains Malaysia for research grant R&D No.
304/PFIZIK/670011. AU thanks Universiti Sains Malaysia for
a Visiting Postdoctoral Fellowship.
Re®nement
2
2
2
o
2
Re®nement on F
2
w = 1/[ꢄ (F ) + (0.042P)
+ 1.1659P]
where P = (Fo + 2F )/3
2
R[F > 2ꢄ(F )] = 0.060
wR(F ) = 0.133
S = 1.13
2
2
2
c
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1608). Services for accessing these data are
described at the back of the journal.
(Á/ꢄ)max < 0.001
Ê
� 3
Áꢅmax = 0.18 e A
Áꢅmin = � 0.23 e AÊ
3
2
015 re¯ections
84 parameters
� 3
H atoms treated by a mixture of
independent and constrained
re®nement
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256±262.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Sheldrick, G. M. (1996). SADABS. University of G oÈ ttingen, Germany.
Sheldrick, G. M. (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison,
Wisconsin, USA.
Table 3
Hydrogen-bonding geometry (A, ) for (II).
Ê
ꢀ
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Tian, J.-Z., Zhang, Z.-G., Yang, X.-L., Fun, H.-K. & Xu, J.-H. (2001). J. Org.
Chem. 66, 8230±8235.
Wasserman, H. H. & Scheffer, J. R. (1967). J. Am. Chem. Soc. 89, 3073.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C16ÐH16Á Á ÁO1
O1ÐH1O1Á Á ÁO3
0.96 (3)
0.78 (3)
2.32 (3)
2.31 (3)
2.700 (4)
2.902 (2)
103 (2)
133 (3)
ii
1
1
2
Symmetry code: (ii) � x; y � 2
;
� z.
ꢁ
o310 Anwar Usman et al.
C
26
H O
18 2
and C22
H O
20 3
Acta Cryst. (2003). C59, o308±o310