Synthesis and structural characterization of (2E,3E)-N1,N 2-Bis(4-chlorobenzylidene)ethane-1,2-diamine

Article abstract of DOI:10.14233/ajchem.2013.12108b

Present compound (2E,3E)-N¹,N²-bis(4- chlorobenzylidene)ethane-1,2-diamine (C₁₆H₁₄C ₁₄N₂, M_r = 305.19) was synthesized and characterized by elemental analysis, FT-IR, ¹H NMR and single crystal X-ray diffraction. The crystal belongs to monoclinic, space group Cc, with a = 10.166(2), b = 10.345(2), c = 26.650(5) ?, β = 91.91(3)°, V = 2801.1(10) ?3, Z = 8, D_c = 1.447 g/cm³, λ = 0.71073 ?, μ(MoK_α) = 0.454 mm^-1, F ₍₀₀₀₎ = 1264. The final refinement gave R = 0.0652, wR(F²) = 0.1582 for 4,578 observed reflections with I > 2σ (I). X-Ray diffraction analysis reveals that the asymmetric unit of the title compound consists of two independent molecules. Each independent molecule adopts an E configuration about the central C=N functional bond. The dihedral angles between the two benzene rings are 2.3(2) and 0.5(2)°, respectively in two independent molecules. The molecules are linked through C- H···Cl hydrogen bonds interactions.

Full text of DOI:10.14233/ajchem.2013.12108b

Asian Journal of Chemistry; Vol. 25, No. 2 (2013), 663-665
http://dx.doi.org/10.14233/ajchem.2013.12108B
Synthesis and Structural Characterization of
1
2E,3E)-N ,N -Bis(4-chlorobenzylidene)ethane-1,2-diamine
2
(
*
ZU-PEI LIANG and JIAN LI
Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, P.R. China
Corresponding author: Tel: +86 536 8877561; E-mail: lzpwfu@163.com
Received: 23 May 2011; Accepted: 11 August 2012)
*
(
AJC-11952
1
2
Present compound (2E,3E)-N ,N -bis(4-chlorobenzylidene)ethane-1,2-diamine (C16
H
14
l4
C N
2
, M
r
= 305.19) was synthesized and charac-
1
terized by elemental analysis, FT-IR, H NMR and single crystal X-ray diffraction. The crystal belongs to monoclinic, space group Cc,
with a = 10.166(2), b = 10.345(2), c = 26.650(5) Å, β = 91.91(3)º, V = 2801.1(10) Å , Z = 8, D
0.454 mm , F(000) = 1264. The final refinement gave R = 0.0652, wR(F ) = 0.1582 for 4,578 observed reflections with I > 2σ(I). X-Ray
3
3
c
= 1.447 g/cm , λ = 0.71073 Å, µ(MoK
α
)
-1
2
=
diffraction analysis reveals that the asymmetric unit of the title compound consists of two independent molecules. Each independent
molecule adopts an E configuration about the central C=N functional bond. The dihedral angles between the two benzene rings are 2.3(2)
and 0.5(2)º, respectively in two independent molecules. The molecules are linked through C-H···Cl hydrogen bonds interactions.
1
Key Words: (2E,3E)-N ,N -Bis(4-chlorobenzylidene)ethane-1,2-diamine, Synthesis, Structure characterization.
2
(0.7 g, 5 mmol) in 20 mL ethanol was added drop by drop, the
INTRODUCTION
solution was stirred magnetically for 1 h at reflux temperature.
After cooling to room temperature, the product was filtered
and dried. Yield 89.2 %. 10 mg of the title compound were
dissolved in 20 mL ethanol and the solution was kept at room
temperature. The single crystal suitable for X-ray determination
was obtained by evaporation from ethanol solution after a
The Schiff bases are used as substrates in the preparation
of a number of industrial and biologically active compounds
1
via ring closure, cycloaddition and replacement reactions .
Schiff bases are known to have biological activities such as
2
-4
5
6
antimicrobial , antitumor and herbicidal properties . They
have also been widely used as versatile ligands involved in
week. Anal. calcd. (%) for C16
H
14
N
2
4
Cl : C 62.95, H 4.59, N
7
-9
various metal chelation reactions to form metal complexes ,
which are very intreresting in many fields, such as catalysis
and enzymatic reactions
9
λ
.18. Found (%): C 63.06, H 4.63, N 9.15. Selected IR (KBr,
-1
1
max, cm ): 1635 (s, C=N), 1416 (s, C-N), 1090 (s, Ar-Cl). H
COCD , ppm): δ = 8.14 (s, 2H), 7.60 (d, 4H),
.35 (d, 4H), 3.90 (m, 4H).
Data collection and structure determination:A selected
1
0,11
12
and magnetism . Recently, a few
NMR data (CD
7
3
3
Schiff base compounds with antibacterial activity have been
4,13-15
1
2
investigated
. In this paper, (2E,3E)-N ,N -bis(4-chloro-
benzylidene)ethane-1,2-diamine was synthesized and its
molecular structure was characterized by elemental analysis,
crystal of the title compound was mounted on a SMART CCD
diffractometer. The reflection data were measured at 298 K,
1
FT-IR, H NMR and X-ray crystallographic techniques.
using a graphite monochromator MoK
radiation with an ω-2θ scan mode. The total reflections were
,917 with 4,578 independent ones (Rint = 0.0679), of which
α
(λ = 0.71073 Å)
EXPERIMENTAL
7
All the reagents were of AR grade and used without fur-
361 were observed with I > 2σ(I). Intensities were corrected
-1
ther purification. IR spectra (4000-400 cm ), as KBr pellets,
for Lorentz and polarization effects and empirical absorption
1
16
were recorded on a Nicolet FT-IR 510P spectrometer. H NMR
and all data were corrected using SADABB program.
spectra were measured with a Bruker ALP 80 nuclear mag-
The structure was solved by direct methods using
17
netic resonance spectrometer (CD
as internal standard).
3
COCD
3
as solvent, TMS
SHELXS-97 program. All the non-hydrogen atoms were
2
refined on F anisotropically by full-matrix least squares
Synthesis of the title compound: To a solution of 1,2-
diamino ethane (0.3 g, 5 mmol) and potassium acetate (0.98
g, 10 mmol) in 10 mL distilled water, 4-chlorobenzaldehyde
method. All hydrogen atoms were placed in the geometrically
calculated positions. The contributions of these hydrogen
atoms were included in the structurefactor calculations. The

664 Liang et al.
Asian J. Chem.
atomic scattering factors and anomalous dispersion corrections
were taken from International Table for X-ray crystallo-
18
graphy . The final least-square cycle gave R = 0.0652 and
2
2
2
ωR = 0.1582 (w = 1/[σ (Fo ) + (0.0882P) + 0.0000P], where
2
2
P = (Fo + 2Fc )/3). S = 1.018, (∆ρ)min = -0.488 and (∆ρ)max
.472 e/Å . CIF file containing complete information on the
=
3
0
studied structure was deposited with CCDC, deposition
number 693623 and is freely available upon request from the
following web site: www.ccdc.cam.ac.uk/data_request/cif
RESULTS AND DISCUSSION
The selected bond distances and bond angles are listed in
Table-1.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 is shown in Fig. 2.
TABLE-1
SELECTED BOND LENGTHS (Å) AND BOND ANGLES (º)
Bond
Length (Å)
1.736(6)
1.746(6)
1.740(6)
1.740(6)
1.268(8)
1.468(7)
1.259(8)
1.4440(7)
1.280(8)
1.459(8)
1.263(7)
1.459(8)
Bond
Angle (º)
117.6(5)
115.9(5)
116.7(5)
116.8(2)
122.9(6)
111.0(4)
110.3(4)
123.7(5)
122.2(6)
110.8(4)
110.2(5)
123.5(6)
Cl(1)-C(3)
Cl(2)-C(14)
Cl(3)-C(19)
Cl(4)-C(30)
N(1)-C(7)
N(1)-C(8)
N(2)-C(10)
N(2)-C(9)
N(3)-C(23)
N(3)-C(24)
N(4)-C(26)
N(4)-C(25)
C(7)-N(1)-C(8)
C(10)-N(2)-C(9)
C(23)-N(3)-C(24)
C(26)-N(4)-C(25)
N(1)-C(7)-C(6)
N(1)-C(8)-C(9)
N(2)-C(9)-C(8)
N(2)-C(10)-C(11)
N(3)-C(23)-C(22)
N(3)-C(24)-C(25)
N(4)-C(25)-C(24)
N(4)-C(26)-C(27)
Fig. 2. View of crystal packing down the a-axis
As seen from Fig. 1, the asymmetric unit of (2E,3E)-
1
2
N ,N -bis(4-chlorobenzylidene) ethane-1,2-diamine consists
of two independent molecules. In the independent molecule,
two 4-chlorobenzaldehyde groups are bridged by ethane-1,2-
diamine via two C=N double bonds in a roughly linear geo-
metry. Each molecule adopts an E configuration about the
central C=N functional bond. The dihedral angles between
the two benzene rings are 2.3(2) and 0.5(2)º, respectively in
two independent molecules.
All the bond lengths and bond angles in the title compound
are within normal ranges and comparable to those in the similar
13,14,19
compounds
. The C7-N1 bond length of 1.268(8) Å, the
C10-N2 bond length of 1.259(8) Å, the C23-N3 bond length
of 1.280(8) Å and the C26-N4 bond length of 1.263(7) Å
conform to the value for a double bond, while the C8-N1 bond
length of 1.468(7) Å, the C9-N2 bond length of 1.440(7) Å,
the C24-N3 bond length of 1.459(8) Å and the C25-N4 bond
length of 1.459(8) Å conform to the value for a single bond.
The C=N bond lengths are close to the corresponding bond
length in N,N'-bis(3- nitrobenzylidene)butane-1,4-diamine
19
[
1.267(3) Å] . The molecules are linked through C-H···Cl
hydrogen bonds interactions (Fig. 2 and Table 2).
TABLE-2
HYDROGEN BOND SCHEMES (Å, º)
D-H···A
C2-H2···Cl4
C29-H29···Cl1
D-H
0.93
0.93
H···A
2.864
2.900
D-A
3.616
3.613
D-H···A
139
135
a
b
Symmetry codes: (a) -1+x, -y, -1/2 + z; (b) 3/2 + x, 1/2-y, 1/2 + z.
ACKNOWLEDGEMENTS
This work was supported by Shandong Provincial Natural
Science Foundation, China (No. ZR2010BM033).
Fig. 1. Molecular structure with atomic numbering scheme

1
2
Vol. 25, No. 2 (2013)
Synthesis and Structural Characterization of (2E,3E)-N ,N -Bis(4-chlorobenzylidene)ethane-1,2-diamine 665
1
1
2. Z. Liu and F.C. Anson, Inorg. Chem., 40, 1329 (2001).
3. Z.P. Liang, J. Li, F.T. Kong, C.H. Lin and X.S. Tai, Chin. J. Struct.
Chem., 28, 628 (2009).
REFERENCES
1
2
.
.
F.D. Karia and P.H. Parsania, Asian J. Chem., 11, 991 (1999).
P.G. More, R.B. Bhalvankar and S.C. Pattar, J. Indian Chem. Soc., 78,
74 (2001).
14. J. Li, Z.P. Liang, F.T. Kong, H. Zhang and X.S. Tai, Chin. J. Struct.
Chem., 28, 577 (2009).
4
3
4
5
6
7
.
.
.
.
.
N.P. Singh, P. Kumar and J. Singh, Asian J. Chem., 24, 5719 (2012).
N. Wang, J.P. Li and Y.L. Pu, Chin. J. Struct Chem., 26, 547 (2007).
S.B. Desai, P.B. Desai and K.R. Desai, Heterocycl. Commun., 7, 83 (2001).
S. Samadhiya and A. Halve, Orient. J. Chem., 17, 119 (2001).
A. Balaban, N. Colak, H. Unver, B. Erk, T.N. Durlu and D.M. Zengin,
J. Chem. Crystallogr., 38, 369 (2008).
15. N.P. Singh, Anu and J. Singh, Asian J. Chem., 25, 455 (2013).
16. G.M. Sheldrick, SADABS, Program for Empirical Absorption Correction
of Area Detector Data, University of Gottingen, Germany (1996).
17. G.M. Sheldrick, SHELXTL V 5.1 Software Reference Manual, Bruker
AXS, Inc., Madison, Wisconsin, USA (1997).
18. Siemens, SMART and SAINT, Area Detector Control and Integration
Software. Siemens Analytical X-Ray Systems, Inc., Madison, Wisconsin,
USA (1996).
8
9
.
.
C.G. Hamaker and B.P. Oberts, J. Chem. Crystallogr., 36, 735 (2006).
J. Chen, X.Y. Xu, J. Gao, Y.H. Li and G.X. Xu, Chin. J. Struct. Chem.,
2
6, 632 (2007).
19. M.H. Habibi, K. Barati, M. Zendehdel, R. W. Harrington and W. Clegg,
Anal. Sci., 23, x61 (2007).
1
1
0. H.J. Kim, W. Kim, A.J. Lough, B.M. Kim and J.A. Chin, J. Am. Chem.
Soc., 127, 16776 (2005).
1. J.P. May, R. Ting, L. Lermer, J.M. Thomas,Y. Roupioz and D.M. Perrin,
J. Am. Chem. Soc., 126, 4145 (2004).