Crystal structure of 3,3-diphenylnaphtho[1,2-c]furan-1(3H)-one

Article abstract of DOI:10.1023/A:1009561909291

The crystal structure of 3,3-diphenylnaphtho[l,2-c]furan-l(3H)-one 2 was determined by X-ray diffraction analysis. It possesses P2₁2₁2₁ (number 19) space group symmetry, with a = 11.922(2), b = 17.142(4), c = 8.429(2) Angstroem, and D_calc = 1.297 mg/m³ for Z = 4.

Full text of DOI:10.1023/A:1009561909291

Journal of Chemical Crystallography, Vol. 29, No. 10, 1999
Crystal structure of 3,3-diphenylnaphtho [1, 2-c] furan-1
(3H)-one
Jie Xue,(1) Jie Sun,(2) and Jian-Hua Xu(1)*
Received October 8, 1999
The crystal structure of 3, 3-diphenylnaphtho[1, 2-c]furan-1(3H)-one 2 was determined by
X-ray diffraction analysis. It possesses P212121 (#19) space group symmetry, with a ϭ 11.922(2),
b ϭ 17.142(4), c ϭ 8.429(2) A, and Dcalc ϭ 1.297 mg/m3 for Z ϭ 4.
˚
KEY WORDS: Radical; single electron transfer; rearrangement; photosensitize.
Introduction
The effect of homoconjugation on the reactivity
and of norcaradiene3d systems). Ohashi and his co-
workers have investigated the influence of homocon-
jugative interaction on the reactivity of cation radicals
of 7-benzhydrylidenenorbornene derivatives.4 In
these investigations, the cation radicals have been
generated by photoinduced single electron transfer
(PET) processes, using cyano-substituted aromatics
(such as 1,4-dicyano-benzene,3c, 4 9, 10-dicyanoanthra-
cene,3b etc.) or quinones (such as 2, 3, 5, 6-tetrachloro-
1, 4-benzoquinone3a, 3b) as an electron acceptor sensi-
tizer.
We report here an investigation on the reactivity
of cation radicals of 7-diphenylmethylenenorbonene
generated in PET reaction initiated by the electron
acceptor sensitizer 2, 4, 6-tetraphenylpyrylium per-
chlorate (TPPϩ). The novel compound 3,3-diphenyl-
naphtho[1, 2-c]furan-1(3H)-one 2 was obtained by
photoinduced electron transfer oxygenation of com-
pound 1 (Scheme 1) and its MS, NMR, IR, and ele-
mental analysis data are in accord with the as-
signed structure.
of carbocations has long been known.1 7-diphenyl-
methylenebenzonorbonene 1 is a molecule in which
there exists a homoconjugative interaction between
the endocyclic and exocyclic olefinic double bonds.
Recently, the reactions of electron–donor com-
pounds with photoexcited acceptors resulting in elec-
tron transfer and the subsequent reactions (re-
arrangement, nucleophilic trapping of the cationic
center by the solvent and trapping of the radical cen-
ter by oxygen, etc.) of the donor cation radicals have
received considerable attention.2 As a result of the
rapid development in the area of single electron
transfer (SET) reactions of organic compounds, the
phenomena of homoconjugation in organic cation
radicals has also been recognized and investigations.
Roth and his co-workers have provided evidence for
the presence of homoconjugative interactions be-
tween nonconjugated olefinic double bonds (as in the
cation radicals of 9-methylenebicyclo[4.2.1]nona-2, 4,
7-triene3a and 7-methylenenorbornadiene3b, 3c) and be-
tween an olefinic bond and a cyclopropane moiety (as
in the cation radicals of 7-methylenequadricyclane3b, 3c
(1) Department of Chemistry, Nanjing University, Nanjing 210093,
P. R. China.
(2) Shang Hai Institute of Organic Chemistry, Chinese Academy
of Science, Shang Hai 200032, P. R. China.
* To whom correspondence should be addressed.
1117
1074-1542/99/1000-1117$16.00/0  1999 Plenum Publishing Corporation

1118
Xue, Sun, and Xu
Table 1. Crystal Data and Structure Refinement
CCDC no.
Color/shape
CCDC-1003/5690
colorless/prismatic
C24H16O2
336.39
293.1
Chemical formula
Formula weight
Temperature, K
Crystal system
Space group
orthorhombic
P212121 (#19)
Unit cell dimensions
˚
a ϭ 11.922(2) A
˚
b ϭ 17.142(4) A
˚
c ϭ 8.429(2) A
˚
Volume, A
1722.4(6)
Z
4
Density (calculated), mg/m3
Ȑcalc, cmϪ1
1.297
0.81
0.810
Absorption coefficient, cmϪ1
Diffractometer/scan
Rigaku AFC7R/Ͷ-2␪ scans
2␪ range for data collection, deg
Reflections measured
Observed reflections
Data/restraints/parameters
Absolute Structure Parameter
Extinction Coefficient
Goodness of Fit Indicator
Final R indices [I Ͼ 2␴(I)]
13.7 - 21.2
2274
1878 [I Ͼ 2␴(I)]
1878/0/236
0.03
93.59908
1.580
R1 ϭ 0.0350, wR2 ϭ 0.0420
Fig. 1. View of the title compound with displacement ellipsoids
at the 50% probability level.
Table 2. Table of Positional Parameters and Their Estimated Standard Deviations
Atom
x
y
z
U(iso)
O1
O2
C1
C2
C3
C4
C5
C6
0.3173(1)
0.4391(1)
0.3642(2)
0.3090(1)
0.2328(1)
0.2341(2)
0.1641(2)
0.1758(2)
0.2553(2)
0.3263(2)
0.4078(2)
0.4190(2)
0.3491(2)
0.2683(2)
0.1241(2)
0.1029(2)
0.0070(2)
Ϫ0.0695(2)
Ϫ0.0517(2)
0.0451(2)
0.2774(2)
0.3788(2)
0.4149(2)
0.3511(3)
0.2514(3)
0.2136(2)
0.21621(8)
0.11939(9)
0.1600(1)
0.1621(1)
0.2215(1)
0.2623(1)
0.2354(1)
0.1873(1)
0.1260(1)
0.1127(1)
0.0532(1)
0.0098(1)
0.0219(2)
0.0781(2)
0.2555(1)
0.3042(1)
0.2951(1)
0.2377(1)
0.1904(1)
0.1995(1)
0.3463(1)
0.3677(1)
0.4451(2)
0.4999(1)
0.4793(1)
0.4024(1)
0.2240(2)
0.1808(2)
0.1312(3)
Ϫ0.0245(2)
Ϫ0.0242(2)
0.1352(2)
Ϫ0.1570(3)
Ϫ0.2856(3)
Ϫ0.2905(2)
Ϫ0.1575(2)
Ϫ0.1655(3)
Ϫ0.3010(4)
Ϫ0.4306(3)
Ϫ0.4261(3)
0.2264(2)
0.3551(3)
0.4454(3)
0.4084(3)
0.2789(3)
0.1877(3)
0.1243(2)
0.1912(3)
0.1847(4)
0.1104(4)
0.0421(4)
0.0499(3)
0.0480(4)
0.0599(4)
0.0448(5)
0.0402(5)
0.0420(5)
0.0420(5)
0.0507(6)
0.0547(6)
0.0490(5)
0.0437(5)
0.0537(6)
0.0686(8)
0.0737(8)
0.0655(7)
0.0436(5)
0.0525(6)
0.0563(6)
0.0581(7)
0.0647(7)
0.0573(6)
0.0468(5)
0.0579(6)
0.0757(8)
0.0810(9)
0.0844(9)
0.0661(7)
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24

3,3-diphenylnaphtho [1,2-c] furan-1(3H)-one
Experimental
1119
˚
Table 3. Selected Bond Distance (A) and Angles (Њ) with esd’s in
Parentheses
A solution of 0.612 g 7-diphenylmethyleneben-
zonorbornene 1 (2.0 mmol) in 40 mL CH2Cl2 was
photolyzed with TPPϩ as sensitizer. The solution was
then irradiated with light ␭ Ͼ 400 nm at room temper-
ature under continuous dry oxygen purging. At the
end of the reaction (TLC monitoring), the solvent
was removed in vacuo and the residue was separated
by flash chromatography on a silica gel column with
petroleum ether (b.p. 60-90ЊC)-ethyl acetate (10:1)
as eluents to give the title compound 2 (200 mg at
yield 30%). Clear, colorless single crystals suitable for
X-ray diffraction analysis were obtained from ethyl
acetate solution.
O1UC1
O1UC4
O2UC1
C1UC2
C2UC3
C3UC4
C4UC13
C4UC19
C1UO1UC4
O1UC1UO2
O1UC1UC2
O2UC1UC2
1.361(2)
1.472(2)
1.207(2)
1.469(3)
1.365(3)
1.515(3)
1.523(3)
1.533(3)
C1UC2UC3
C1UC2UC8
C3UC2UC8
C2UC3UC4
C2UC3UC5
C4UC3UC5
O1UC4UC3
O1UC4UC13
O1UC4UC19
C3UC4UC13
C3UC4UC19
C13UC4UC19
108.3(2)
128.8(2)
122.9(2)
109.8(2)
120.9(2)
129.3(2)
102.1(1)
106.4(1)
107.9(2)
113.8(2)
112.6(2)
113.1(2)
111.4(1)
120.9(2)
108.2(2)
130.9(2)
All measurements were made on a Rigaku
AFC7R diffractometer with graphite monochro-
mated Mo-KͰ radiation. The data were corrected for
Lorentz and polarization. The structure was solved
by direct methods5 and expanded using Fourier tech-
niques.6 Refinement was by full-matrix least-squares
methods with anisotropic displacement parameters
for all non-H-atoms and isotropic displacement pa-
rameters for H atoms. All calculations were per-
formed using the teXsan7 crystallographic software
package of Molecular Structure Corporation. A sum-
mary of crystal data and structure refinement is pro-
vided in Table 1, the refined atomic coordinates are
given in Table 2.
O1UC4UC3UC2 are 3.5(2) and Ϫ2.0(2)Њ, respec-
tively, meanwhile, the largest deviation being
˚
0.023(2) A for the C1 atom. The O2 atom lies 0.083
˚
A above this plane. The C1uO2 bond distance of
˚
1.207(2) A (Table 3) agrees well with those in related
compounds8 and with the value for a CuO double
9
˚
bond (1.202 A) reported by Allen et al. The bond
˚
˚
lengths of 1.361 (2) A for O1UC1 and 1.472(2) A
for O1UC4 indicate that the former is a OUC(uO)
single bond and the later is a (CU)CUO single
bond.9 In the naphtho [1,2-c]furan framework of the
molecule, the three fused rings are in a plane within
estimated limits of error.
The dihedral angles between rings A and B, A
and C, A and D, B and C, B and D, and C and
D are 3.74, 104.89, 61.24, 108.27, 59.55, and 99.26Њ,
respectively. The plane A and plane B are nearly
coplanar with a small dihedral angle of 3.74Њ. Plane
C and plane D are almost perpendicular to each other
with a dihedral angle of 99.26Њ in order to minimize
the steric hindrance between the H-atoms on the two
benzene rings.
Spectroscopic data
Colorless prisms, m.p. 168ЊC, ␯max/cmϪ1 3050,
1740, 1580, 1490, 1445, 1200, 1180, 1120, 955, 827,
783, 755, 700; ͳH/ppm (500 MHz, CDCl3) 7.32–7.38
(10H, m, ArH); 7.59–7.63 (2H, m, ArH), 7.72 (1H,
t, J 7.5, ArH), 7.93 (1H, d, J 8.2, ArH), 8.11 (1H, d,
J 8.2, ArH), 9.07 (1H, d, J 8.2, ArH); m/z(%) 336
(Mϩ, 33), 259 (72), 231 (100), 165 (6). (Found: C,
85.60; H, 4.91. C24 H16O2 requires C, 85.71; H, 4.76).
Acknowledgment
This project was supported by the National Nat-
ural Science Foundation of China (29772016).
Results and discussion
Figure 1 shows the ORTEP drawing of the title
compound 2 with the atom-numbering scheme. Posi-
tional parameters and their estimated standard devia-
tions are listed in Table 2. Selected bond lengths and
angles are listed in Table 3. The five atoms forming
the heterocyclic furanone ring all lie in the same
plane. The torsion angles C1UO1UC4UC3 and
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Xue, Sun, and Xu
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