Synthesis and crystal structure of 1,4-bis{[(2'-Thenylaminoformyl)phenoxyl] methyl}benzene

Article abstract of DOI:10.14233/ajchem.2013.16062

A novel salicylamide derivative i.e., 1,4-bis{[(2'-thenylaminoformyl) phenoxyl]methyl}benzene with the m.f. C₃₂H₂₈N ₂O₄S₂ has been synthesized and the crystal structure was determined by single crystal X-ray diffraction. There are strong intramolecular hydrogen bonding between the amide nitrogen atoms and the ethereal oxygen atoms which stabilized the structure to form a trans configuration. Furthermore the title compound are linked by intermolecular C9-H9O1 hydrogen bonds into an infinite 1D chain parallel to the bc plane.

Full text of DOI:10.14233/ajchem.2013.16062

Asian Journal of Chemistry; Vol. 25, No. 17 (2013), 10004-10006
http://dx.doi.org/10.14233/ajchem.2013.16062
Synthesis and Crystal Structure of 1,4-bis{[(2'-Thenylaminoformyl)phenoxyl]methyl}benzene
*
LI WANG, XIAO-RUN WANG, GUO-QUAN CHENG,YUN-QIAO PENG and XUE-QIN SONG
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
*
Corresponding author: Fax: +86 931 4938755; Tel: +86 931 8843385; E-mail: songxq@mail.lzjtu.cn; songxueqin001@163.com
(
Received: 18 July 2013;
Accepted: 30 October 2013)
AJC-14325
A novel salicylamide derivative i.e., 1,4-bis{[(2'-thenylaminoformyl)phenoxyl]methyl}benzene with the m.f. C32
H
28
N
2
O
4
2
S has been
synthesized and the crystal structure was determined by single crystal X-ray diffraction. There are strong intramolecular hydrogen bonding
between the amide nitrogen atoms and the ethereal oxygen atoms which stabilized the structure to form a trans configuration. Furthermore the
title compound are linked by intermolecular C9-H9…O1 hydrogen bonds into an infinite 1D chain parallel to the bc plane .
Key Words: Salicylamide derivative, Synthesis, trans-Configuration, Crystal structure.
INTRODUCTION
EXPERIMENTAL
In the last decade, synthesis of salicylamide-derived
Phenylamine was obtained from Alfa Aesar Co. Other
commercially available chemicals were of analytical grade
and were used without further purification. X-ray single
crystal structure was determined on a Bruker Smart 1000 CCD
area detector. Melting points were determined on a Kofler
apparatus and the thermometer was uncorrected.
ligands have been carried out because of their attractive sensiti-
zation of lanthanide luminescence as well as construction of
1
novel metal-organic frameworks . So far a series of salicylamide
ligands which incorporated different backbones and terminal
2-5
groups have been synthesized . We are systematically studying
the structure and the photophysical properties of complexing
salicylamide ligands of capable of sensitizing Eu(III) and
Synthesis of the title compound: The synthetic route for
the title compound is shown in Scheme-I. 2-Thenylsalicylamide
was prepared according to the literature procedure with minor
6
-8
Tb(III) emission recently . Herein, we report the synthesis
and crystal structure of 1,4-bis{[(2'-thenylaminoformyl)-
phenoxyl]methyl}benzene.
9
modifications and 1,4-bis-bromomethyl-benzene were prepared
10
according to the literature .
S
Br
(HCHO)n
NH
O
O
3
3% HBr/HAc Br
K CO
2
3
O
O
CH COCH
3
3
O
OH
o
S
S
90 C
+
H N
2
N
H
HN
OCH3
OH
O
S
Scheme-I: Synthetic route of the title compound

Vol. 25, No. 17 (2013)
Synthesis and Crystal Structure of 1,4-bis{[(2'-Thenylaminoformyl)phenoxyl]methyl}benzene 10005
To a solution of 2-thenylsalicylamide ( 2.33g, 10.5 mmol)
in dry acetone was added 1.52 g (11 mmol) dried K CO and
the mixture was stirred for 0.5 h at room temperature, then
.32 g (5 mmol) 1,4-bis-bromomethyl-benzene in 20 mL of
dry acetone was added dropwise in 0.5 h and the resulting
solution stirred and heated to reflux for 24 h. After cooling
down, inorganic salts were separated by filtration and the
solvent removed from the filtrate under reduced pressure. The
crude product was recrystallized with ethyl acetate to give a
white solid 2.43 g, Yield 86 %, m.p. 175-176 °C.
The title compound (0.057 g, 0. 1 mmol) was dissolved
in ethyl acetate (10 mL) and sealed for crystallization at room
temperature. After about 2 weeks colourless crystals suitable
for analysis were obtained.
X-Ray structure determination: The single crystal of
the title compound with the approximate dimensions of 0.15
mm × 0.10 mm × 0.08 mm was placed on a Bruker Smart 1 000
CCD area detector. The reflections were collected using a
2
3
1
TABLE-1
CRYSTAL DATA AND STRUCTURE
REFINEMENT FOR THE TITLE COMPOUND
graphite monochromated MoK
α
radition (λ = 0.71073 Å) at
2
96 (2) K. The structure was solved by using the program
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
32 28 2 4 2
C H N O S
SHELXL-97 and Fourier difference techniques and refined
by the full-matrix least-squares method on F . All non-hydrogen
564.91
296(2)
0.71073
2
atoms were subjected to anisotropic refinement and all
hydrogen atoms were added in idealized positions and refined
isotropically. Crystal data and details of the refinement are
summarized in Table-1, representative bond lengths (Å) and
angles (°) are presented in Table-2. CCDC reference numbers
monoclinic
Space group
P 2 /c
1
Cell dimensions, (Å, deg)
a = 10.0826(17), b = 17.546(3),
c = 8.2262(14),
α = 90, β = 107.244(3), γ = 90
1389.9(4)
2
1.3498
0.218
9
50108.
3
Volume (Å )
Z
RESULTS AND DISCUSSION
X-ray crystallographic analysis revealed the crystal
3
Density (calculated) (mg/m )
Absorption coefficient (mm )
-
1
structure of the title compound. The structure is shown in
Fig. 1. It is worth noting that there are strong intramolecular
hydrogen bonding between the amide nitrogen atoms and the
etheric oxygen atoms with O2…N1 separations ca. 2.815 Å
and N1-H1…O2 angles averaging 134.3° which stabilized
the structure to form a trans configuration (Fig. 2). Further-
more, the title compound are linked by intermolecular
C9-H9…O1 hydrogen bonds into an infinite 1D chain parallel
to the bc plane, as illustrated in Fig. 3 and hydrogen bonds
data are summarized in Table-3.
F
(000)
593.1083
Index ranges
-13 ≤ h ≤ 7, -23 ≤ k ≤ 22,
-10 ≤ l ≤ 10
θ (°)
2.11-25.00
2425/1740
2425/1/250
0.0352
1.0726
R1 = 0.0405, wR = 0.0988
Reflections collected/unique
Data/restraints/parameters
Independent reflections (Rint
Goodness of fit indicator
Final R indices [I > 2σ(I)]
R indices (all data)
)
2
2
R1 = 0.0601, wR = 0.0988
TABLE-2
SELECTED BOND LENGTHS (Å) AND ANGLES (º) FOR THE TITLE COMPOUND
Bond
Lengths Bond Lengths Bond
1.365(2) C(11)-O(1) 1.228(2) C(6)-C(7)
1.439(2)
Lengths
1.382(3)
O(2)-C(5)
O(2)- C(4)
N(1)-C(11)
N(1)-C(12)
C(5)- C(10)
C(5)-C(6)
C(11)-C(10)
C(9)-C(10)
C(9)-C(8)
C(2)-C(4)
C(2)-C(1)
C(2)-C(3)
1.498(3)
1.395(3)
1.375(3)
1.498(3)
1.368(3)
1.365(3)
C(8)-C(7)
1.371(3)
1.490(3)
1.362(15)
1.685(4)
1.320(3)
1.647(5)
1.334(2)
1.447(3)
1.402(2)
1.384(3)
1.381(3)
1.493(17)
C(13)-C(12)
C(13)-C(14)
C(13)-S(1)
C(16)-C(15)
C(16)-S(1)
C(1)-C(3)
C(15)-C(14)
Bond
Angles
Bond
Angles
1
1
1
1
21.26(15)
20.64(18)
16.32(16)
23.09(17)
120.2(2)
119.6(2)
120.3(2)
128.6(7)
120.9(2)
110.4(7)
119.5(3)
104.6(6)
111.38(18)
105.40(16)
121.4(2)
121.0(2)
114.1(10)
91.3(2)
C(4)-O(2)-C(5)
C(12)-N(1)-C(11)
C(10)-C(5)-O(2)
C(6)-C(5)-O(2)
C(6)-C(5)-O(10)
O(1)-C(11)-N(1)
C(10)-C(11)-N(1)
C(10)-C(11)-O(1)
C(8)-C(9)-C(10)
C(11)-C(10)-C(5)
C(9)-C(10)-C(5)
C(9)-C(10)-C(11)
C(1)-C(2)-C(4)
C(3)-C(2)-C(4)
C(3)-C(2)-C(1)
C(7)-C(6)-C(5)
C(7)-C(8)-C(9)
C(8)-C(7)-C(6)
C(14)-C(13)-C(12)
S(1)-C(13)-C(12)
S(1)-C(13)-C(14)
S(1)-C(16)-C(15)
C(14)-C(15)-C(16)
C(13)-C(12)-N(1)
C(2)-C(4)-O(2)
C(3)-C(1)-C(2)
120.58(17)
120.60(19)
118.73(16)
120.66(17)
122.0(2)
126.28(16)
1
1
17.36(18)
16.35(17)
C(1)-C(3)-C(2)
C(15)-C(14)-C(13)
C(16)-S(1)-C(13)
1
1
20.5(2)
21.9(2)
117.57(19)

10006 Wang et al.
Asian J. Chem.
TABLE-3
DATA FOR HYDROGEN-BONDING INTERACTIONS (Å, º)
D-H···A
N1-H1···O2
C9-H9···O1
d(D-H)
0.91(2)
0.95(2)
d(H···A)
1.91(2)
2.48(2)
d(D···A)
2.625(2)
3.301(3)
∠D-H···A
134.3(19)
144.7(16)
Symmetry code
2-x, -y,2z
Fig. 3. View of the infinite 1D chain motif of the title compound (hydrogen atoms, except those forming hydrogen bonds, are omitted for clarity)
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science
Foundation of China (Grant No. 21161011) and Gansu Natural
Science Foundation of China (Grant No. 1212RJZA038).
REFERENCES
1
2
3
4
.
.
.
.
J. Zhang, Y. Tang, N. Tang, M.Y. Tan, W.S. Liu and K.B. Yu, J.
Chem. Soc. Dalton Trans., 832 (2002).
T. Terai, H. Ito, K. Kikuchi and T. Nagano, Chem. Eur. J., 18, 7377
(
2012).
Y.W. Wang, Y.L. Zhang, W. Dou, A.J. Zhang, W.W. Qin and W.S.
Liu, J. Chem. Soc. Dalton Trans., 39, 9013 (2010).
Fig. 1. Molecule structure of the title compound (hydrogen atoms are
omitted for clarity)
P.K. Mohapatra, M. Iqbal, D.R. Raut, W. Verboom, J. Huskens and
S.V. Godbole, J. Chem. Soc. Dalton Trans., 41, 360 (2012).
S.V. Eliseeva and J.C.G. Bünzli, Chem. Soc. Rev., 39, 189 (2010).
X.Q. Song, X.Y. Zhou, W.S. Liu, W. Dou, J.X. Ma, X.L. Tang and
J.R. Zheng, Inorg. Chem., 47, 11501 (2008).
5
6
.
.
7
8
.
.
.
X.Q. Song, X.G. Wen, W.S. Liu and D.Q. Wang, J. Solid State Chem.,
1
83, 1 (2010).
X.Q. Song, L. Wang, M.M. Zhao, G,Q. Cheng, X.R. Wang and Y.Q.
Peng, Inorg. Chim. Acta, 402, 156 (2013).
K. Michio, Bull. Chem. Soc. Jpn, 49, 2679 (1976).
9
1
0. Z. Jiri, P. Magdalena, H. Petr and T. Milos, Synthesis, 1132 (1994).
Fig. 2. View of the intramolecular hydrogen-bonding interactions of
the title compound (hydrogen atoms, except those forming
hydrogen bonds are omitted for clarity)