Synthesis, characterization and crystal structure of trans-2-(2- Hydroxyphenyl)-1-nitroethylene

Article abstract of DOI:10.14233/ajchem.2014.16446

The nitroalkene compound, namely trans-2-(2-hydroxyphenyl)-1-nitroethylene (I), has been successfully synthesized from the condensation of 2-hydroxybenzaladehyde with nitromethane. It was characterized by elemental analysis, 1H NMR spectrum and single-cry

Full text of DOI:10.14233/ajchem.2014.16446

Asian Journal of Chemistry; Vol. 26, No. 8 (2014), 2475-2478
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.16446
Synthesis, Characterization and Crystal Structure of trans-2-(2-Hydroxyphenyl)-1-nitroethylene
1
2
2,*
2
2
2,*
YUN-FENG LIU , SHENG-NAN LIU , PEI-HUA ZHAO , XIN-HANG LI , WEN-JUN LIANG and YA-QING LIU
1College of Public Health, Shanxi Medical University, Taiyuan 030001, P.R. China
2Research Center for Engineering Technology of Polymeric Composites of Shanxi Province, College of Materials Science and Engineering,
North University of China, Taiyuan 030051, P.R. China
*Corresponding authors: E-mail: zph2004@163.com, gczx2012@gmail.com
Received: 30 September 2013;
Accepted: 10 December 2013;
Published online: 15 April 2014;
AJC-15052
The nitroalkene compound, namely trans-2-(2-hydroxyphenyl)-1-nitroethylene (I), has been successfully synthesized from the condensation
of 2-hydroxybenzaladehyde with nitromethane. It was characterized by elemental analysis, 1H NMR spectrum and single-crystal X-ray
diffraction analysis. Compound (I) crystallizes in the triclinic, space group P-1 with a = 5.2270(5), b = 11.2130(10), c = 13.6080(13) Å,
α = 71.224(18), β = 84.47(3), γ = 81.20(3)°, V = 745.29(16) Å3, Z = 4, C8H7NO3, Mr = 165.15, Dc = 1.472 g/cm3, F(000) = 344, µ(MoKα)
= 0.115 mm-1, the final R1 = 0.0500 and wR2 = 0.1358 for 2309 observed reflections [I > 2σ(I)]. Moreover, the crystal structure of (I) is
stabilized by the intermolecular O-H···O hydrogen bonds, the π-π stacking interactions and the C-H···O short contacts, which extend the
molecules into an infinite three-dimensional network.
Keywords: Nitroalkene, Synthesis, Crystal Structure, Intermolecular interaction.
INTRODUCTION
EXPERIMENTAL
The nitroalkene compounds have attracted much attention
from a synthetic point of view because they are recognized as
one of the most valuable building blocks in the organic synthesis.
For example, the nitro functionality with the multiple reactivity
undergoes conversion to 1,3-dipoles, oxidation to carboxylic
acids and reduction to hydroxylamines1-3; furthermore, the C=C
double bond activated by the nitro group reacts with various
nucleophiles by means of Michael addition reaction4-6. Mean-
while, the nitroalkenes and their derivatives display diverse
biological activities such as insencticidal activities, anticancer
activities and anti-HVI-1 activities7-9, etc. For better understan-
ding of the relationship between molecular structures and
biological activities, the detailed investigation on the synthesis
and structures of such compounds seems very important.
In continuation of the study on such important com-
pounds10-13, we herein report the synthesis, characterization
and crystal structure of a nitroalkene compound, namely trans-
2-(2-hydroxyphenyl)-1-nitroethylene (I) (Scheme-I).
All the chemicals were of reagent grade and used without
further purification. Melting points were determined on aYRT-
3 apparatus and are uncorrected. Elemental analyses for carbon,
hydrogen and nitrogen were performed on a Perkin-Elmer 240
C analyzer. 1H NMR spectrum was obtained on a Bruker AV-
400 instrument (400 MHz) using TMS as an internal standard
and CDCl3 as solvent.
Synthetic procedure: 2-Hydroxylbenzaladehyde (1.22 g,
10 mmol), nitromethane (1.36 mL, 25 mmol) and methanol
(4.20 mL) are added to a three-neck round bottomed flask
and cooled to 0 °C. While maintaining the internal reaction
temperature between 0-15 °C, aqueous 1 M NaOH (25 mL,
25 mmol) is added by an addition funnel and the mixture is
stirred for 15 min. Ice water mixture (17.50 mL) is added and
the reaction is stirred at 0 °C for 0.5 h. The reaction mixture is
slowly added to aqueous 8M HCl (16.80 mL, 134 mmol) and
allowed to stir until the reaction is confirmed complete by
TLC. After the reaction mixture is filtered and recrystallized
from ethanol, the title compound (I) was afforded as the
brown-red solid (0.71 g, yield of 43 %). m.p.: 134-135 °C.
Anal. Calcd. (%) for C8H7NO3: C, 58.18, H, 4.27, N, 8.48.
Found (%): C, 58.27, H, 4.38, N, 8.35. 1H NMR (400 MHz,
CDCl3, TMS) δ/ppm: 8.14 (d, J = 13.6 Hz, 1H, = CH-a),
7.96 (d, J = 13.6 Hz, 1H, =CH-b), 7.44 (d, J = 7.2 Hz, 1H,
PhH-c), 7.36 (t, J = 7.2 Hz, 1H, PhH-e), 7.02 (t, J = 7.2 Hz,
NO2
OH
(I)
Scheme-I

2476 Liu et al.
Asian J. Chem.
1H, PhH-d), 6.86 (d, J = 7.2 Hz, 1H, PhH-f), 5.61 (s, 1H,
OH-g).
Structure of the title compound (I): The single crystal
of the title compound (I) was obtained by slow diffusion of n-
hexane to the acetonitrile solution of (I), which was crystallized
as air-stable brown-red crystals. Crystallographic and
refinement parameters are listed in Table-1. The selected bond
lengths and angles are given in Tables-2 and 3, respectively.
The molecular structure of (I) is depicted in Fig. 2. The
crystal packing diagram of (I) is shown in Fig. 3.
Crystal structure determination: Single crystals of the
title compound (I) suitable for X-ray diffraction analysis were
grown by slow evaporation of the acetonitrile/hexane solution
at 5 °C. The single crystal with dimensions of 0.28 × 0.26 ×
0.12 mm for (I) was mounted on a Rigaku Saturn CCD area
deterctor. Data were collected at 113(2) K for (I) by using a
graphite monochromator with MoKα radiation (λ = 0.71075
Å). A total of 6966 reflections were collected in the range of
1.583º = θ = 27.874º by using an the ω-φ scanning mode, of
which 3445 were unique with Rint = 0.0521 and 2309 were
observed with I > 2σ(I). The structures were solved by direct
methods using the SHELXS-97 program14 and refined by
full-matrix least-squares techniques (SHELXL-97)15 on F2.
Hydrogen atoms were located by using the geometric method.
The final R = 0.0500, wR = 0.1358 (w = 1/[σ2(Fo)2 + (0.0678P)2
+ 0.0000P], where P = (Fo2 + 2Fc2)/3), S = 0.97, (∆/σ)max
=
0.001, (∆ρ)max = 0.272 and (∆ρ)min = -0.288 e/Å3. 3445 (Rint =
0.0521).
RESULTS AND DISCUSSION
Fig. 2. Molecular structure of (I) with 30 % probability thermal ellipsoids
The elemental analyses of the title compound (I) are in
good agreement with the supposed compositions of C8H7NO3.
The H NMR data of (I) are well attributed as displayed in
Fig. 1.
1
As depicted in Fig. 2, the title compound (I) displays a
trans configuration about the C=C double bond. The average
400 MHz, CDCl3
c
f
b
NO2
d
a
e
OH g
CDCl3
a
b
g
f
d
c
e
8.00
7.50
7.00
6.50
6.00
5.50
ppm (t1)
Fig. 1. 1H NMR spectrum of (I)

Vol. 26, No. 8 (2014)
Synthesis, Characterization and Crystal Structure of trans-2-(2-Hydroxyphenyl)-1-nitroethylene 2477
TABLE-2
SELECTED BOND LENGTHS (Å) FOR (I)
Bonds
Dist.
O(2)-N(1)
O(3)-N(1)
N(1)-C(8)
C(7)-C(8)
C(2)-C(7)
O(1)-C(1)
1.2409(19)
1.2248(18)
1.429(2)
1.336(2)
1.448(2)
1.366(2)
TABLE-3
SELECTED BOND ANGLES (°) FOR (I)
Angles
(°)
O(3)-N(1)-O(2)
O(3)-N(1)-C(8)
O(2)-N(1)-C(8)
C(3)-C(2)-C(1)
C(3)-C(2)-C(7)
C(1)-C(2)-C(7)
C(8)-C(7)-C(2)
C(7)-C(8)-N(1)
O(1)-C(1)-C(2)
121.97(15)
120.52(15)
117.51(14)
117.98(16)
123.17(15)
118.85(15)
126.46(16)
119.51(15)
117.45(16)
Fig. 3. Crystal packing diagram of (I) along the α-axis
bond lengths and angles (Table-2 and 3) are in agreement with
those observed in the previously reported nitroethylenes10-13
.
conjugated with the benzene ring and the nitro group17. Further-
more, the dihedral angle between the C(7)/C(8)/N(1)/O(1)/
O(2) plane (r.m.s deviation 0.0388 Å) and the C(1)-C(6) plane
(r.m.s. deviation 0.0048 Å) is 4.1°, which suggests that the
nitroethylene unit is well planar with the 2-hydroxyphenyl
moiety. This is because that the significant level of π-electron
delocalization in the molecular system leads to the planarity
of the molecule19. In addition, the C(7)-C(8)-N(1) bond angle
(119.51(15)°) is shorter than the C(8)-C(7)-C(2) bond angle
(126.46(16)°), probably due to the intramolecular C-H···O
hydrogen bond between the hydrogen atom of the ethylene
moiety and the oxygen atom of the hydroxyl group.
As shown in Fig. 3, the title molecules are stabilized by
the three kinds of intermolecular interactions as follows: (i)
the intermolecular O-H···O hydrogen bonds between the H
atoms of the hydroxyl group with the O atoms of the nitro
group are observed in adjacent molecules, in which the bond
length is 2.191 Å; (ii) there are π-π stacking interactions
involving the benzene rings of two adjacent molecules, where
the two rings are parallel to each other with the centroid-to-
centroid separation of 4.308 Å. (iii) the C-H···O short contacts
between the H atom of the benzene ring and the O atom of the
nitro group exit in adjacent molecules19,20, in which the distance
is 2.455 Å; Consequently, these intermolecular interactions
extend the nitroethylene molecules into an infinite three-
dimensional network.
The C(7)=C(8) bond length (1.336(2) Å) is close to the isolated
C=C bond (1.337 Å)16, conforming it is a typical double bond.
The C(8)-N(1) bond length (1.429(2) Å) and the C(2)-C(7)
one (1.448(2) Å) is shorter than the normal C-N single bond
(1.47 Å)17 and the normal C-C single bond (1.46 Å)18, respec-
tively, indicating that C(7)=C(8) double bond are simultaneously
TABLE-1
CRYSTAL DATA AND STRUCTURAL REFINEMENT FOR (I)
Parameters
Values
Empirical formula
Formula weight
Crystal system
Unit cell dimensions
a (Å, °)
C8H7NO3
165.15
Triclinic
5.2270(5)
b (Å, °)
c (Å, °)
11.2130(10)
13.6080(13)
Unit cell angles (°)
α
71.224(18)
84.47(3)
81.20(3)
745.29(16)
4
β
γ
Volume (Å3)
Z
Temperature (K)
Space group
Wavelength (Å)
Calculated density (g cm-3)
Absorption coefficient ? (mm-1)
F(000)
113(2)
P-1
0.71075
1.472
0.115
344
Conclusion
Crystal size (mm3)
θ range for data collection (°)
0.280 x 0.260 x 0.120
1.583 - 27.874
In summary, the nitroalkene compound [trans-2-(2-
hydroxyphenyl)-1-nitroethylene (I)] has been synthesized and
structurally characterized elemental analysis and H NMR
spectrum. Particularly, the molecular structure of (I) was unequi-
vocally determined by single-crystal X-ray diffraction analysis,
in which the C=C double bond is in a trans configuration in
the solid state. In addition, there are intermolecular O-H···O
hydrogen bonds, π-π stacking interactions and C-H···O short
contacts in the crystal structure of (I), which link the title
molecules into an infinite three-dimensional network.
-6 < = h < = 6, -14 < = k< = 14,
-17 < = l < = 17
Limiting indices
1
Reflection collected
6966
Independent reflection
Completeness to θmax (%)
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
3445 (Rint = 0.0521)
98.3
3445/0/225
0.970
R1 = 0.0500, wR2 = 0.1283
R1 = 0.0674, wR2 = 0.1358
Largest diff.e peak and hole (e A-3) 0.272 and -0.288

2478 Liu et al.
Asian J. Chem.
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