Synthesis and crystal structures of Trans -2-(2-methoxyphenyl)-1- nitroethylene and trans -1-hydroxymethyl-2-(2-methoxyphenyl)-1-nitroethylene dichloromethane hemisolvate

Article abstract of DOI:10.1080/15421406.2013.821645

Two nitroalkene compounds, namely trans-2-(2-methoxyphenyl)-1-nitroethylene (1) and trans-1-hydroxymethyl-2-(2-methoxyphenyl)-1-nitroethylene dichloromethane hemisolvate (2), have been synthesized and structurally characterized by elemental analysis,

Full text of DOI:10.1080/15421406.2013.821645

This article was downloaded by: [University of West Florida]
On: 28 December 2014, At: 20:24
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Molecular Crystals and Liquid Crystals
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gmcl20
Synthesis and Crystal Structures
of trans-2-(2-Methoxyphenyl)-1-
nitroethylene and trans-1-
Hydroxymethyl-2-(2-methoxyphenyl)-1-
nitroethylene Dichloromethane
Hemisolvate
Pei-Hua Zhao a & Yun-Feng Liu b
a Research Center for Engineering Technology of Polymeric
Composites of Shanxi Province, College of Materials Science and
Engineering , North University of China , Taiyuan , P. R. China
b College of Public Health , Shanxi Medical University , Taiyuan , P.
R. China
Published online: 16 Dec 2013.
To cite this article: Pei-Hua Zhao & Yun-Feng Liu (2013) Synthesis and Crystal Structures of
trans-2-(2-Methoxyphenyl)-1-nitroethylene and trans-1-Hydroxymethyl-2-(2-methoxyphenyl)-1-
nitroethylene Dichloromethane Hemisolvate, Molecular Crystals and Liquid Crystals, 587:1, 113-120,
DOI: 10.1080/15421406.2013.821645
To link to this article: http://dx.doi.org/10.1080/15421406.2013.821645
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,

systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Mol. Cryst. Liq. Cryst., Vol. 587: pp. 113–120, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1542-1406 print/1563-5287 online
DOI: 10.1080/15421406.2013.821645
Synthesis and Crystal Structures
of trans-2-(2-Methoxyphenyl)-1-nitroethylene
and trans-1-Hydroxymethyl-2-(2-methoxyphenyl)-1-
nitroethylene Dichloromethane
Hemisolvate
PEI-HUA ZHAO1 AND YUN-FENG LIU2,∗
1Research Center for Engineering Technology of Polymeric Composites
of Shanxi Province, College of Materials Science and Engineering, North
University of China, Taiyuan, P. R. China
2College of Public Health, Shanxi Medical University, Taiyuan, P. R. China
Two nitroalkene compounds, namely trans-2-(2-methoxyphenyl)-1-nitroethylene (1) and
trans-1-hydroxymethyl-2-(2-methoxyphenyl)-1-nitroethylene dichloromethane hemisol-
vate (2), have been synthesized and structurally characterized by elemental analysis, 1H
(13C) NMR spectra, and single-crystal X-ray diffraction. The nitroethylene molecules
in (1) and (2) adopt a trans configuration about the C C double bonds. The crystal
structures of (1) and (2) are stabilized by the C H···O short contacts, and particularly
for (2) intermolecular O–H···O hydrogen bonds are also observed.
[Supplemental materials are available for this article. Go to the publisher’s online
edition of Molecular Crystals and Liquid Crystals to view the free supplemental file:
Crystallographic data for the structural analysis have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication number CCDC 892535 and
892537 for the title compounds (1) and (2), respectively. Copies of the data can be
obtained free of charge at http://www.ccdc.cam.ac.uk/conts/retrieving. html, or from
the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk.]
Keywords Crystal structures; intermolecular interaction; nitroethylene; synthesis
Introduction
The nitroalkene compounds are generally prepared by an aldol type C C bond forma-
tion process, in specific Henry condensation of carbonyl compounds with a nitroalkane
to β-nitroalcohol followed by dehydration [1, 2]. Most particularly, the aromatic ni-
troalkene compounds have been proved to be a significant class of the nitroalkenes, which
possess diverse biological activities such as molluscicidal activities [3, 4], insencticidal
activities [4], antimicrobial activities [5, 6], anticancer activities [7], anti-HIV-1 activi-
ties [8], and so on. Detailed study on the synthesis and structures of such compounds
∗Address correspondence to Yun-Feng Liu, College of Public Health, Shanxi Medical University,
Taiyuan 030001, P. R. China. Tel.: +86-351-3559669. E-mail: lyfsl@163.com
113

114
P.-H. Zhao and Y.-F. Liu
Figure 1. The molecular structures of the title compounds (1) and (2).
seems very important to better understand the relationship between molecular structures
and biological activities. Based on the above information and as a continuation of our
studies on such compounds, we herein report that two nitroalkene compounds, trans-2-(2-
methoxyphenyl)-1-nitroethylene (1) and trans-1-hydroxymethyl-2-(2-methoxyphenyl)-1-
nitroethylene dichloromethane hemisolvate (2), have been synthesized and their structures
were characterized using the single-crystal X-ray diffraction method as well as spectro-
scopic techniques. Their molecular structures are shown in Fig. 1. In this context, we now
wish to present the detailed crystal structure analyses of the title compounds (1) and (2)
based on X-ray diffraction.
Experimental
Materials and Instruments
All the chemicals were of reagent grade and used without further purification. Melting
points were determined on a YRT-3 apparatus and are uncorrected. Elemental analyses for
carbon, hydrogen, and nitrogen were performed on a Perkin-Elmer 240C analyzer. 1H (13C)
NMR spectra were obtained on a Bruker Avance 400 MHz spectrometer.
Synthetic Procedures
The synthetic route of the title compounds (1) and (2) is presented in Scheme 1.
Scheme 1. Synthetic route for the title compounds (1) and (2).
Synthesis of trans-2-(2-Methoxyphenyl)-1-nitroethylene (1)
2-Methoxybenzaladehyde (2.72 g, 20.0 mmol), nitromethane (2.72 mL, 50.0 mmol), and
methanol (8.40 mL) are added to a three-neck round bottomed flask and cooled to 0◦C.
While maintaining the internal reaction temperature between 0◦C and 15◦C, aqueous 1 M
NaOH (50.00 mL, 50.0 mmol) is added by an addition funnel and the mixture is stirred
for 15 min. Ice water mixture (35.00 mL) is added and the reaction is stirred at 0◦C for

Crystal Structures of Two Nitroethylene Compounds
115
30 min. The reaction mixture is slowly added to aqueous 8 M HCl (33.50 mL, 268.0 mmol)
and allowed to stir until the reaction is confirmed complete by TLC. The reaction mixture
is filtered and recrystallized from ethanol to give the yellow solid (0.86 g, yield of 24%).
Mp: 45◦C–46◦C. Anal. Calcd. (%) for C9H9NO3: C, 60.33, H, 5.06, N, 7.82. Found (%):
C, 60.19, H, 5.35, N, 7.65. 1H NMR (400 MHz, CDCl3, TMS) δ/ppm: 8.18 (d, 1H), 7.89
(d, 1H), 7.46 (m, 2H), 7.00 (m, 2H), 3.96 (s, 3H). 13C NMR (100.6 MHz, CDCl3, TMS)
δ/ppm: 159.5, 138.3, 135.5, 133.5, 132.5, 121.1, 119.2, 111.4, 55.7.
Synthesis of trans-1-Hydroxymethyl-2-(2-methoxyphenyl)-1-nitroethylene
Dichloromethane Hemisolvate (2)
To a stirred solution of (1) (0.90 g, 5.0 mmol) in THF (10.00 mL) at room temperature
was added imidazole (0.34 g, 100 mol%) followed by anthranilic acid (0.07 g, 10 mol%).
Formaldehyde (38% aqueous, 10.00 mL) was then added and the reaction mixture was
stirred at room temperature. After the completion of the reaction (confirmed by TLC
analysis), the reaction mixture was acidified with water (25.00 mL) and the aqueous layer
was extracted with EtOAc (3 × 50.00 mL). The combined organic layers were dried over
anhydrous sodium sulfate and concentrated in vacuo. The residue was separated by silica
gel column chromatography eluting with EtOAc/pet. ether to afford a bright-yellow solid
(0.50 g, yield of 48%). Mp: 38◦C–39◦C. Anal. Calcd. (%) for C10H11NO4: C, 57.41, H,
5.30, N, 6.70. Found (%): C, 57.66, H, 5.54, N, 6.50. 1H NMR (400 MHz, CDCl3, TMS)
δ/ppm: 8.18 (s, 1H), 7.39 (t, 1H), 7.14 (d, 1H), 7.09 (s, 1H), 7.03 (d, 1H), 4.70 (s, 2H), 3.85
(s, 3H), 2.52 (br s, 1H). 13C NMR (100.6 MHz, CDCl3, TMS) δ/ppm: 158.4, 148.9, 134.0,
132.8, 130.7, 121.0, 120.5, 110.8, 57.1, 55.7.
Single-Crystal X-ray Diffraction
Single crystals of the title compounds (1) and (2) suitable for X-ray diffraction analyses
were grown by slow evaporation of the CH2Cl2/hexane solution at 5◦C. Two single crystals
with dimensions of 0.20 mm × 0.18 mm × 0.12 mm for (1) and 0.16 mm × 0.14 mm ×
0.12 mm for (2) were mounted on a Rigaku Saturn CCD area deterctor. Data were collected
at 113(2) K by using a graphite monochromator with MoKα radiation (λ 0.71073 Å) for
(1) and CuKα radiation (λ = 1.54187 Å) for (2) in the ω-φ scanning mode. Absorption
corrections were performed by SADABS program [9]. The structures were solved by direct
methods using the SHELXS-97 program [10] and refined by full-matrix least-squares
techniques (SHELXL-97) [11] on F2. Hydrogen atoms were located using the geometric
method. Details of crystal data, data collection, and structure refinement for (1) and (2) are
listed in Table 1. Selected bond lengths and angles for (1) and (2) are given in Table 2.
Hydrogen bonding interactions for (2) are summarized in Table 3.
Results and Discussion
Spectral Analyses
The synthesized nitroethylene compounds were characterized by elemental analysis and
1H (13C) NMR spectra. Their structures were unambiguously determined using X-ray
diffraction analysis. The elemental analysis and NMR spectra have been in good agreement
with the formulae proposed by the X-ray crystallography for (1) and (2), respectively.

116
P.-H. Zhao and Y.-F. Liu
Table 1. Crystal data and structural refinement details for (1) and (2)
Compounds
(1)
(2)
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
C9H9NO3
179.17
113(2)
0.71073
Monoclinic
P2(1)/n
C21H24Cl2N2O8
503.32
113(2)
1.54187
Monoclinic
C12/c1
Space group
Unit cell dimensions (Å, ◦)
a = 5.415(3),
b = 16.813(8),
c = 9.430(5), α = 90,
β = 99.579(6), γ = 90
846.5(7), 4
a = 24.450(2),
b = 9.7630(9),
c = 9.9760(10), α = 90,
β = 96.523(16), γ = 90
2255.4(4), 4
1.482
Volume (Å3), Z
Calculated density (g
1.406
cm−3
)
Absorption coefficient μ
(mm−1
F(000)
0.107
3.044
)
376
1048
Crystal size (mm3)
θ Range for data collection
(◦)
0.20 × 0.18 × 0.12
0.16 × 0.14 × 0.12
2.42–26.02
3.82–72.13
Limiting indices
−6< = h< = 6, −20<
= k< = 18, −11< =
l< = 11
−28< = h< = 30,
−12< = k< = 8,
−12< = l< = 12
10663
Reflection collected
7736
Independent reflection
Completeness to θmax (%)
Data/restraints/parameters
Goodness of fit on F2
1677 (Rint = 0.0525)
2192 (Rint = 0.0311)
99.9
98.3
1677/0/119
2192/2/158
1.003
1.164
Final R indices [I > 2σ(I)]
R1 = 0.0347, wR2 =
R1 = 0.0582, wR2 =
0.0828
0.1294
R indices (all data)
R1 = 0.0469, wR2 =
0.0856
R1 = 0.0604, wR2 =
0.1326
Largest difference peak
0.141 and −0.268
0.473 and −0.636
and hole (e A−3
CCDC number
)
892535
892537
Crystal Structure Description of the Title Compound (1)
As depicted in Fig. 2, the nitroethylene molecule in (1) displays a trans configuration about
the C C double bond. The bond lengths and angles (Table 2) are in agreement with those
observed in the reported similar species [12−22]. The C8 C9 bond length (1.3248(19)
Å) is close to the isolated C C bond (1.337 Å) [12], conforming it is a double bond. The
C9 N1 bond length (1.4389(17) Å) and the C8 C7 bond length (1.4525(19) Å) are shorter
than the normal C N single bond (1.472 Å) [12] and the normal C C single bond (1.46
Å) [23], respectively, mainly due to the strong π-electron delocalization of the molecular

Crystal Structures of Two Nitroethylene Compounds
117
Table 2. Selected bond lengths (Å) and bond angles (◦) for (1) and (2)
Compound (1)
O(2)-N(1)
1.2283(15)
N(1)-C(9)
1.4389(17)
C(7)-C(8)
1.4525(19)
O(3)-N(1)
1.2401(15)
O(1)-C(1)
1.4347(17)
C(8)-C(9)
1.3248(19)
O(2)-N(1)-O(3) 122.70(11) C(2)-O(1)-C(1) 118.06(10) C(6)-C(7)-C(8) 122.70(13)
O(2)-N(1)-C(9) 120.61(12) C(6)-C(7)-C(2) 118.27(12) C(2)-C(7)-C(8) 118.99(12)
O(3)-N(1)-C(9) 116.69(12) C(8)-C(9)-N(1) 120.22(13) C(9)-C(8)-C(7) 125.91(13)
Compound (2)
O(3)-N(1)
O(4)-N(1)
1.2369(18)
1.2333(18)
N(1)-C(8)
1.470(2)
C(2)-C(7)
C(7)-C(8)
1.462(2)
1.343(2)
O(1)-C(10)
1.440(2)
O(4)-N(1)-O(3) 122.96(14) O(1)-C(1)-C(2) 115.42(14) C(8)-C(7)-C(2) 125.71(14)
O(4)-N(1)-C(8) 119.62(13) O(1)-C(1)-C(6) 124.18(15) C(7)-C(8)-N(1) 117.15(14)
O(3)-N(1)-C(8) 117.42(13) N(1)-C(8)-C(9) 114.39(13) C(7)-C(8)-C(9) 128.34(15)
Table 3. Hydrogen bond lengths (Å) and bond angles (◦) for (2)
D H···A
d(D H)
d(H···A)
2.03(3)
2.05(3)
d(D···A)
2.843(3)
2.854(3)
∠DHA
O(2) H(2A)···O(2)a
0.83(3)
0.84(3)
167(4)
160(4)
O(2) H(2B)···O(2)b
Symmetry codes: a –x, –y, –z+1; b –x, +y, –z+1/2.
Figure 2. Crystal structure of (1) with 30% probability thermal ellipsoids.

118
P.-H. Zhao and Y.-F. Liu
Figure 3. Crystal packing diagram of (1) along the c-axis.
system [14]. Furthermore, the dihedral angle between the C2 C7 plane (r.m.s. deviation
0.0038 Å) and the N1/O2/O3/C8/C9 plane (r.m.s deviation 0.0132 Å) is 6.1o, suggesting
that the nitroethylene moiety is almost coplanar with the o-methoxyphenyl moiety. This is
because the significant level of π-electron delocalization in the molecular system leads to
the planarity of the molecule [14]. In addition, the N1 O3 bond length is about 0.012 Å
longer than the N1 O2 bond length, possibly owing to the weak interaction between O
atom of the nitro group and the H atom of the phenyl group [12].
As shown in Fig. 3, the crystal packing of (1) is stabilized by the C H···O short
contacts involving the H atoms of the phenyl and vinyl groups as well as the O atoms
of the nitro group [13, 18]. For example, the O3Q atom from the nitro group has a short
nonbonded contact with the H atoms attached to the phenyl C6Y and vinyl C9Y atoms (the
distance is 2.530 Å and 2.428 Å, respectively) between the adjacent molecules within a
one-dimensional layered network.
Crystal Structure Description of the Title Compound (2)
As depicted in Fig. 4, the nitroethylene molecule in (2) adopts a trans configuration about
the C C double bond. The bond lengths and angles (Table 2) are within normal ranges,
and are comparable to those observed in (1). The C7 C8 bond length is 1.343(2) Å,
which is a typical double bond and it is longer than that in (1). The C8 N1 bond length
(1.470(2) Å) and the C7 C2 bond length (1.462(2) Å) are very close to the corresponding
normal single bond length [12, 23], which means that the degree of the π-electron delo-
calization in (2) is remarkably weaker than those in (1). Furthermore, the dihedral angle
between the C1 C6 plane (r.m.s. deviation 0.0096 Å) of the o-methoxyphenyl moiety
and the N1/O3/O4/C7/C8/C9 plane (r.m.s deviation 0.0137 Å) of the 1-hydroxymethyl-1-
nitroethylene moiety is 42.9o, which is sharply larger than the corresponding angle of (1).
This indicates that the molecule of (2) is much less planar compared to that of (1), prob-
ably because of the steric repulsion and intermolecular interactions of the hydroxymethyl
substituent, which is a bigger group with respect to the ethylenic hydrogen atom [22]. In
addition, the N1 O3 bond length (1.2369(18) Å) and the N1 O4 bond length (1.2333(18)

Crystal Structures of Two Nitroethylene Compounds
119
Figure 4. Crystal structure of (2) with 30% probability thermal ellipsoids.
Å) in (2) are almost identical, which is different from the nonequivalent N O bond lengths
of the nitro group in (1).
As shown in Fig. 5, there are some similar C H···O short contacts like (1). For instance,
the one between the O4D atom of the nitro group and the H atom linked to the methoxyl
C10O atom, which is 2.625 Å, exits in the parallel adjacent molecules; meanwhile, the
other from the O10 atom of the methoxyl group to the H atom attached to the phenyl
C6H atom, which is 2.560 Å, is found in the almost perpendicular adjacent molecules.
Additionally, intermolecular O H···O hydrogen bonds are observed in the crystal structure
of (2) (Table 3), which is not the case in (1). As a result, the two kinds of intermolecular
interactions link the molecule into an infinite three-dimensional network (Fig. 5).
Figure 5. Crystal packing diagram of (2) along the c-axis.

120
P.-H. Zhao and Y.-F. Liu
Conclusions
In summary, two nitroalkene compounds [trans-2-(2-methoxyphenyl)-1-nitroethylene (1)
and trans-1-hydroxymethyl-2-(2-methoxyphenyl)-1-nitroethylene dichloromethane hemi-
solvate (2)] have been synthesized and structurally characterized by elemental analysis and
1H (13C) NMR spectra. Particularly, the molecular structures of (1) and (2) were unequivo-
cally determined by single-crystal X-ray diffraction analysis, where the C C double bond
is in a trans configuration in the solid state. In addition, the C H···O short contacts exist
in the crystal structures of (1) and (2).
Acknowledgments
This work was financially supported by Shanxi Province Science Foundation for Youths
(No. 2012021007-4) and National Natural Science Foundation of China (No. 51102216).
References
[1] Luo, M., & Yan, B. (2010). Tetrahedron Lett., 51, 5577.
[2] Rana, S., Mallick, S., & Parida, K. M. (2011). Ind. Eng. Chem. Res., 50, 2055.
[3] Louis-Ferdinand, R. T., & Fuller, G. C. (1970). Toxicol. Appl. Pharmacol., 16, 668.
[4] Latif, N., Mishriky, N., Girgis N. S., & Arnos, S. (1980). Indian J. Chem., 19B, 301.
[5] Canoira, L., Gonzalo-Rodriguez, J. G., Subirats, J. B., Escario, J. A., Jimenez, I., & Martinez-
Fernandez, A. R. (1989). Eur. J. Med. Chem., 24, 39.
[6] Milhazes, N., Calheiros, R., Marquez, M. P. M., Garrido, J., Cordeiro, M. N. D. S., Rodrigues,
C., Quinteira, S., Novais, C., Peixe, L., & Borges, F. (2006). Bioorg. Med. Chem., 14, 4078.
[7] Mohan, R., Rastogi, N., Namboothiri, I. N. N., Mobin, S. M., & Panda, D. (2006). Bioorg. Med.
Chem., 14, 8073.
[8] Cheng, P., Jiang, Z. Y., Wang, R. R., Zhang, X. M., Wang, Q., Zheng, Y. T., Zhou, J., & Chen,
J. J. (2007). Bioorg. Med. Chem. Lett., 17, 4476.
[9] Sheldrick, G. M. (1996). SADABS: Program for Empirical Absorption Correction of Aera
Detector Data, University of Go¨ttingen: Go¨ttingen.
[10] Sheldrick, G. M. (1997). SHELXS-97: Program for Crystal Structure Solution, University of
Go¨ttingen: Go¨ttingen.
[11] Sheldrick, G. M. (1997). SHELXL-97: Program for Crystal Structure Refinement, University of
Go¨ttingen: Go¨ttingen.
[12] Cameron, T. S., Cowley, D. J., & Thompson, J. E. (1974). J. Chem. Soc. Perkin Trans. II., 774.
[13] Pedireddi, V. R., Sarmab, J. P., & Desiraju, G. R. (1992). J. Chem. Soc. Perkin Trans. II., 311.
[14] Nesterov, V. N., Kislyi, V. P., Timofeeva, T. V., Antipin, M. Y., & Semenov, V. V. (2000). Acta
Crystallogr., C56, e107.
[15] Xu, H., Sun, H. S., & Xu, N. (2009). Acta Crystallogr., E65, o1691.
[16] Jing, L. H. (2009). Acta Crystallogr., E65, o2521.
[17] Jing, L. H. (2009). Acta Crystallogr., E65, o2809.
[18] Kennedy, A. R., Kipkorir, Z. R., Muhanji, C. I., & Okoth, M. O. (2010). Acta Crystallogr., E66,
o2984.
[19] Ren, Y. H., & Zhu, R. T. (2010). Acta Crystallogr., E66, o2249.
[20] Zhao, P. H., Feng, Z. H., Zhang, M., Liu, Y. Q., & Zhao, G. Z. (2011). Acta Crystallogr., E67,
o3505.
[21] Zhao, P. H., Hao, E. J., Liu, Y. Q., & Zhao, G. Z. (2012). Acta Crystallogr., E68, o1742.
[22] Radulovic´, N. S., Bogdanovic´, G. A., Blagojevic´, P. D., Dekic´, V. S., & Vukic´evic´, R. D. (2011).
J. Chem. Crystallogr., 41, 545.
[23] Dewar, M. J. S., & Thiel, W. (1977). J. Am. Chem. Soc., 99, 4907.