Synthesis and structural characterization of N-Phenyl-5-norbornene-2,3-dicarboximide

Article abstract of DOI:10.14233/ajchem.2015.18068

The compound N-phenyl-5-norbornene-2,3-dicarboximide (C₁₅H₁₃NO₂, M_r = 239.26) was synthesized and characterized by single crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a = 9.7534(13), b = 21.395(2), c = 12.0647(14) ?, β = 108.7020(10)°, V = 2384.6(5) ?³, Z = 8, Dc = 1.333 g/cm³, λ = 0.71073 ?, μ(MoK_α) = 0.089 mm^-1, F(000) = 1008. The final refinement gave R = 0.0741, wR (F²) = 0.1676 for 4,199 observed reflections with I > 2α(I). The structure of the title compound comprises a racemic mixture of chiral molecules containing four stereogenic centres. X-ray diffraction analysis reveals that the cyclohexane ring tends towards a boat conformation, the tetrahydrofuran ring and the dihydrofuran ring adopt envelope conformations. The dihedral angles between the pyrrolidine-2,5-dione plane and the aromatic ring are 65.5 (2)° and 54.9 (2)°, respectively in the two molecules.

Full text of DOI:10.14233/ajchem.2015.18068

Asian Journal of Chemistry; Vol. 27, No. 8 (2015), 2806-2808
A
SIAN
J
OURNAL OF HEMISTRY
C
http://dx.doi.org/10.14233/ajchem.2015.18068
Synthesis and Structural Characterization of N-Phenyl-5-norbornene-2,3-dicarboximide
*
ZU PEI LIANG , JIAN LI and XIAO RU PAN
College of Chemistry, Chemical and Environmental Engineering, Weifang University, Weifang 261061, P.R. China
*Corresponding author: Tel: +86 536 8877561; E-mail: lzpwfu@163.com
Received: 23 May 2014;
Accepted: 15 September 2014;
Published online: 27 April 2015;
AJC-17136
The compound N-phenyl-5-norbornene-2,3-dicarboximide (C15H13NO2, Mr = 239.26) was synthesized and characterized by single crystal
X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a = 9.7534(13), b = 21.395(2), c = 12.0647(14) Å, β =
108.7020(10) °,V = 2384.6(5) Å3, Z = 8, Dc = 1.333 g/cm3, λ = 0.71073 Å, µ(MoKα) = 0.089 mm-1, F(000) = 1008. The final refinement gave
R = 0.0741, wR (F2) = 0.1676 for 4,199 observed reflections with I > 2α(I). The structure of the title compound comprises a racemic
mixture of chiral molecules containing four stereogenic centres. X-ray diffraction analysis reveals that the cyclohexane ring tends towards
a boat conformation, the tetrahydrofuran ring and the dihydrofuran ring adopt envelope conformations. The dihedral angles between the
pyrrolidine-2,5-dione plane and the aromatic ring are 65.5 (2)° and 54.9 (2)°, respectively in the two molecules.
Keywords: N-Phenyl-5-norbornene-2,3-dicarboximide, Synthesis, Structural characterization, X-ray diffraction.
INTRODUCTION
EXPERIMENTAL
The polymers made of norbornene dicarboximide have
good thermal stability and low dielectric constant. They have
been used in large-scale integrated circuit1. The process of
norbornene dicarboximide monomer being synthesized
consists of two steps. Norbornene dianhydride was dissolved
in toluene and the solution of amine/toluene was dropped into
above solution, the reaction of norbornene dianhydride and
amine was kept for 3 h at 60 °C, filtered and filter cake dried.
And then the above intermediate was added to acetic anhydride
containing sodium acetate, the solution was heated to reflux
for 4 h, filtered, washed and filter cake dried2,3.
All the reagents were ofAR grade and used without further
purification.
The intermediates I were prepared according to the
literatural report4. The synthesis of N-phenyl-5-norbornene-
2,3-dicarboximide II is described as a mixture of exo-
bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride (0.328 g,
2 mmol) and aniline (0.186 g, 2 mmol) in methanol (8 mL)
was stirred for 4 h at room temperature and then refluxed for
1 h. After cooling the precipitate was filtered and dried, the
title compound was obtained. The crude product of 20 mg
was dissolved in methanol of 10 mL. The solution was filtered
to remove impurities and then the filtrate was left for crystalli-
zation at room temperature. The single crystal suitable for X-
ray determination was obtained by evaporation from the
methanol solution after 6 d.
In this paper, the title compound N-phenyl-5-norbornene-
2,3-dicarboximide was synthesized in one-pot mode with high
yields (Scheme-I) and its molecular structure was investigated
by X-ray crystallographic techniques.
Data collection and structure determination:A selected
crystal of the title compound was mounted on a SMART CCD
diffractometer. The reflection data were measured at 298 K,
using a graphite monochromator MoKα (λ = 0.71073 Å)
radiation with an ω-2θ scan mode. The total reflections were
11,552 with 4,199 independent ones (Rint = 0.1539), of which
325 were observed with I > 2σ(I). Intensities were corrected
for Lorentz and polarization effects and empirical absorption
and all data were corrected using SADABB5 program.
The structure was solved by direct methods using
SHELXS-976 program. All the non-hydrogen atoms were
Scheme-I

Vol. 27, No. 8 (2015)
Synthesis and Structural Characterization of N-Phenyl-5-norbornene-2,3-dicarboximide 2807
refined on F2 anisotropically by full-matrix least squares
method. All hydrogen atoms were placed in the geometrically
calculated positions. The contributions of these hydrogen
atoms were included in the structurefactor calculations. The
atomic scattering factors and anomalous dispersion corrections
were taken from International Table for X-ray crystallography7.
The final least-square cycle gave R = 0.0741 and ωR = 0.1676
TABLE-1
ATOMIC COORDINATES (× 104) AND
THERMAL PARAMETERS (Å2 × 103)
Atom
N(1)
N(2)
O(1)
O(2)
O(3)
O(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
x
y
Z
U(eq)
39(1)
40(1)
58(1)
70(1)
54(1)
71(1)
41(1)
43(2)
45(2)
41(1)
48(2)
54(2)
58(2)
57(2)
63(2)
41(1)
58(2)
68(2)
79(2)
72(2)
51(2)
40(1)
46(2)
44(2)
40(1)
44(2)
48(2)
48(2)
46(2)
52(2)
42(2)
48(2)
60(2)
67(2)
60(2)
49(2)
6596(5)
1684(5)
8023(4)
4921(5)
3110(4)
559(5)
6163(2)
6382(2)
6147(2)
5936(2)
6564(2)
6451(2)
5883(3)
5774(3)
5163(2)
5218(2)
5079(2)
5610(3)
5565(3)
4999(3)
4575(3)
6805(3)
6955(3)
7579(4)
8040(4)
7881(3)
7262(3)
6703(3)
6648(3)
7197(2)
7235(2)
7895(2)
7885(2)
7846(2)
7837(2)
8246(3)
5836(2)
5852(3)
5334(3)
4794(3)
4773(3)
5303(3)
7028(4)
3806(4)
8949(4)
5278(4)
2652(4)
5210(4)
8100(5)
6240(5)
6796(5)
8033(5)
8828(6)
8649(7)
7588(7)
7034(6)
8095(6)
6788(5)
5972(6)
5743(7)
6329(8)
7161(7)
7387(6)
3475(5)
4772(5)
5147(5)
4292(5)
3769(5)
3045(6)
3770(6)
4979(5)
4837(6)
3219(5)
2034(5)
1489(6)
2093(8)
3268(7)
3831(6)
2
(w = 1/[σ (Fo2) + (0.0712P)2 + 0.0000P], where P = (Fo2 +
2Fc2)/3). S = 1.012, (∆ρ)min = -0.250 and (∆ρ)max = 0.244 e/Å3.
7214(6)
5641(6)
5630(6)
6698(6)
5756(6)
4719(7)
3786(7)
4193(6)
4764(7)
6812(6)
7459(6)
7630(7)
7164(8)
6555(8)
6368(6)
2740(6)
1440(7)
2387(6)
3250(6)
2879(6)
1301(6)
554(6)
RESULTS AND DISCUSSION
The atomic coordinates and equivalent isotropic thermal
parameters for the non-H atoms in the title compound are given
in Table-1 and the selected bond distances and bond angles in
Table-2.A displacement ellipsoid plot with atomic numbering
scheme is shown in Fig. 1 and a perspective view of the crystal
packing in the unit cell in Fig. 2.
1597(6)
2795(7)
956(6)
232(6)
-421(6)
-403(7)
289(7)
971(7)
TABLE-2
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º)
Bond
Length (Å)
1.376(7)
1.377(7)
1.433(7)
1.385(7)
1.399(7)
1.429(7)
1.213(6)
1.199(6)
1.198(6)
1.219(7)
1.527(8)
1.315(9)
1.521(8)
1.516(8)
1.308(8)
1.513(8)
Bond
Angle (º)
112.4(5)
123.4(5)
123.9(4)
112.3(5)
124.1(5)
123.6(5)
124.1(5)
123.5(5)
108.2(6)
107.0(5)
93.4(4)
124.0(5)
123.9(5)
107.3(5)
107.7(5)
93.7(4)
N(1)-C(2)
N(1)-C(1)
N(1)-C(10)
N(2)-C(17)
N(2)-C(16)
N(2)-C(25)
O(1)-C(1)
O(2)-C(2)
O(3)-C(16)
O(4)-C(17)
C(5)-C(9)
C(6)-C(7)
C(8)-C(9)
C(20)-C(24)
C(21)-C(22)
C(23)-C(24)
C(2)-N(1)-C(1)
C(2)-N(1)-C(10)
C(1)-N(1)-C(10)
C(17)-N(2)-C(16)
C(17)-N(2)-C(25)
C(16)-N(2)-C(25)
O(1)-C(1)-N(1)
O(2)-C(2)-N(1)
C(7)-C(6)-C(5)
C(6)-C(7)-C(8)
C(8)-C(9)-C(5)
O(3)-C(16)-N(2)
O(4)-C(17)-N(2)
C(22)-C(21)-C(20)
C(21)-C(22)-C(23)
C(23)-C(24)-C(20)
Fig. 1. Molecular structure with atomic numbering scheme
genic centres. As seen from Fig. 1, the cyclohexane ring tends
towards a boat conformation and the cyclopentene ring and
the cyclopentane ring adopt envelope conformations. The
dihedral angles between the pyrrolidine-2,5-dione plane and
the aromatic ring are 65.5 (2)° and 54.9 (2)°, respectively in
Fig. 2. View of crystal packing down the c-axis
The asymmetric unit of the title compound contains two
molecules. The structure of the title compound comprises a
racemic mixture of chiral molecules containing four stereo-

2808 Liang et al.
Asian J. Chem.
the two molecules. In one molecule, the mean planes C3/C4/
C5/C8 and C5/C6/C7/C8 form dihedral angles of 59.7 (3) and
52.0 (3)º, respectively with the mean plane C5/C8/C9. While
in another one, the mean planes C18/C19/C20/C23 and C20/
C21/C22/C23 form dihedral angles of 60.7 (3) and 51.8 (3)º,
respectively with mean plane C20/C23/C24.
As seen from Table-2, the bond lengths and bond angles
are as expected. In 7-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxi-
mide group, C6-C7 and C6-C7 double bond lengths are
1.315(9) Å and 1.308(8) Å, respectively. The other C-C bonds
are normal single bonds with bond lengths of 1.488(8)-
1.558(8) Å. The crystal structure is stabilized by a strong π-π
stacking interactions from the existence of benzene ring8.
REFERENCES
1. B.Y. Liu, Y. Li, L. Zhang, W. Yan and S. Yao, J. Appl. Polym. Sci., 103,
3003 (2007).
2. A.P. Contreras,A.M. Cerda and M.A. Tlenkopatchev, Macromol. Chem.
Phys., 203, 1811 (2002).
3. K. Díaz, J. Vargas, L.F. Del Castillo, M.A. Tlenkopatchev and M.
Aguilar-Vega, Macromol. Chem. Phys., 206, 2316 (2005).
4. H. Kwart and J. Burchuk, J. Am. Chem. Soc., 74, 3094 (1952).
5. G.M. Sheldrick, SADABS, Program for Empirical Absorption Correction
of Area Detector Data, University of Gottingen, Germany (1996).
6. G.M. Sheldrick, SHELXTL V 5.1 Software Reference Manual, Bruker
AXS, Inc., Madison, Wisconsin, USA (1997).
7. Siemens, SMART and SAINT, Area Detector Control and Integration
Software. Siemens Analytical X-Ray Systems, Inc., Madison, Wisconsin,
USA (1996).
8. B.Q. Su, J. Chem. Crystallogr., 37, 87 (2007).
ACKNOWLEDGEMENTS
This work was supported byWeifang University Provincial
Natural Science Foundation, China (No. 2014Z02).