Synthesis, crystal structure, theoretical calculation, specific heat capacity, and thermodynamic properties of 4,4'-bis(3-N-methoxyformyl thioureido)-diphenyloxide

Article abstract of DOI:10.1002/cjoc.201090317

4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide was prepared via reaction of 4,4'-diaminodiphenyl alter with potassium sulfocyanate and ethyl chloroacetate in ethyl acetate. The single crystal of the title compound was cultured by slow evaporation me

Full text of DOI:10.1002/cjoc.201090317

FULL PAPER
Synthesis, Crystal Structure, Theoretical Calculation, Specific
Heat Capacity, and Thermodynamic Properties of
4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide
a(张新瑜)
*
Zhang, Xinyu
Huang, Jie ,a(黄洁)
Song, Jirongb(宋纪蓉)
Xu, Kangzhenga(徐抗震)
Ban, Qixuna(班琦勋)
a Department of Chemical Engineering/Shaanxi Key Laboratory of Physico-Inorganic Chemistry,
Northwest University, Xi'an, Shannxi 710069, China
b Conservation Technology Department, the Palace Museum, Beijing 100009, China
4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide was prepared via reaction of 4,4'-diaminodiphenyl alter
with potassium sulfocyanate and ethyl chloroacetate in ethyl acetate. The single crystal of the title compound was
cultured by slow evaporation method at room temperature. The crystal structure was determined with X-ray dif-
fractometer. It is a monoclinic crystal, space group C2/c with a＝0.95911(19) nm, b＝0.75922(15) nm, c＝
－
3
2.7161(5) nm, α＝90°, β＝97.675 (3)°, γ＝90°, V＝1.9601(7) nm3, Z＝4, Dc＝1.472 g•cm , F(000)＝904, µ＝
－
1
0.311 cm , R1＝0.0367, wR2＝0.1408. The specific heat capacity of the title compound was determined with con-
tinuous Cp mode of mircocalorimeter. The thermal behavior of the title compound was studied under a
non-isothermal condition by DSC method.
Keywords X-ray diffraction, acylthiourea, thermochemistry, single-molecule studies
Introduction
a Bruker SMART APEXII diffractiometer.
Heterocyclic thiourea compounds are an important
branch in heterocyclic compounds. Because of the ex-
cellent anti-bacterium,1 favorable bioactivity and struc-
ture stabilization, many thiourea compounds as a
new-style pesticide are been studied and synthesized for
these years.2 Dithioure compounds are the selective
recognitive amonic receptors which have the an-
ion-binding site because of containing four acidic N—H
protons.3,4 Especially. through years’of research on
these compounds, we found that these thioureas have
several active centers and can form polyligand com-
plexes with metals easily.5-7 These metals complexes are
broadly useful.8 Recently, designing and synthesizing of
bithioure receptors have become the focus of subject
research in supramolecular chemistry.9-12 In this paper,
we analyzed the crystal structure, specific heat capacity
and thermal behavior of title compound.
Composing 4,4'-bis(3-N-methoxyformyl thioureido)-
diphenyloxide
Under dry condition, 35 mL CH3COOC2H5 and
1.9436 g KSCN were added into a three neck flasks.
Then, in ventilation 1.4 mL ClCOOCH3 was added
dropwise into the solution with agitation. The solution
was kept reacting for 2 h with stirring under reflux at 70
℃. After filtrating the hot solution to get rid of KCl,
1.2615 g 4,4'-2-aminophenyloxide was added into the
filtrate followed by 4 h reaction under reflux. The white
precipitate was filtered, washed with distilled water, and
dried in vacuum at 60 ℃. Single crystals were obtained
by recrystallization from the solvent of dimethyl for-
mamide for 5 d at room temperature. Yield 80%, m.p.
210—213 ℃; IR (KBr) v: 3425.7, 3190.56, 1724.64,
1242.40, 1172.51, 1037.38 cm － 1. Anal. calcd for
C18H18N4O5S2: C 49.77, H 4.147, N 12.9; found C 49.75,
H 3.975, N 12.55.
Experimental
Determination of the specific heat capacity
Reagents and apparatus
The specific heat capacity of the title compound was
All chemicals were of A.R. grade. IR spectrum was
determined on EQUINX55 with KBr presser bit. Ele-
mental analysis was performed on a VarioELШ ele-
mental analyzer. X-ray diffration data were collected on
determined by a continuous Cp mode within 283—353
K at a heating rate of 0.15 K•min－ on Micro-DSCIII
1
(Seteram, France). The Micro-calorimeter was cali-
brated with α-Al2O3 (calcined), its math expression was
*
E-mail: huangjie@nwu.edu.cn
Received March 22, 2010; revised April 24, 2010; accepted May 13, 2010.
Project supported by the Xi'an Scientific and Technical Plan Foundation (No.YF07106).
1902
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1902— 1906

Thermodynamic Properties of 4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide
1
1
3
C /(J•g－ •K－ ) 0.1839 1.9966 10－ T
tions were collected, of which 1747 were independent
(Rint ＝0.0195). The structure was solved by direct
method and Fourier synthesis method, and C2/c was
corrected with full-matrix least-squares procedure. All
non-H atoms were refined anisotropically and hydrogen
atoms were placed in the geometrically calculated posi-
tions. The final R1＝0.0367 and wR2＝0.1408. The
structural plots were drawn with SHELXTL-97 software
package.
＝
＋
×
p
(283.3 K
T
353 K)
≤ ≤
within 283 and 353 K. The standard heat capacity at
－
1
298.15 K was determined as 79.44 J•mol , which is in
an excellent agreement with the value reported in the
literature (79.02 J•mol ).
－
1
Thermal decomposition condition
The crystal data and structural parameters are listed
in Table 1. The bond lengths and angles are listed in
Table 2. The torsion angles are listed in Table 3. The
hydrogen bonds are listed in Table 4. The molecular
structure with atomic labeling scheme is shown in Fig-
ure 1, crystal packing of the molecule in Figure 2.
The DSC and TG-DTG experiments for the title
compounds were performed using a model Q600SDT
(TA, USA) under a nitrogen atmosphere, at a flow rate
－
1
of 100 mL•min . The sample mass was about 0.7 mg.
The heating rates used 10 ℃•min－ from ambient tem-
1
perature to 500 ℃. The temperature and heat were cali-
brated using pure indium and tin particles. The DSC and
TG-DTG curves obtained under the same conditions
overlap with each other, indicating that the reproduci-
bility of tests was satisfactory.
Table 1 Crystal data and structure refinement for the title com-
pound
Formula
Mr
C18H18N4O5S2 γ/(°)
90
434.48
V/nm3
1.9601(7)
4
Results and discussion
λ/nm
0.071073
Z
Dc/(g•cm－
)
1.472
904
3
Crystal structure
Crystal system Monoclinic
Space group
a/nm
C2/c
F(000)
A single crystal of the title compound with dimen-
sions of 0.31 mm×0.26 mm×0.16 mm was selected
for X-ray determination. The intensity data were re-
corded at room temperature by a Bruker SMART APEX
IICCD X-ray diffractometer equipped with a graph-
ite-monochromatic Mo Kα radiation (λ＝0.071073 nm)
in the range of 1.51°≤θ≤25.10°, a total of 4706 reflec-
µ/cm－
0.311
1.51 to 25.10
0.999
0.0367
0.1408
1
0.95911(19)
0.75922(15)
2.7161(5)
90
b/nm
θ range/(°)
GOF
c/nm
α/(°)
R1
β/(°)
97.675（3）
wR2
Table 2 Selected bond lengths (10－ 1 nm) and angles (°) for the title compound
Bond
Length
1.663(2)
1.339(3)
1.423(2)
0.86
Bond
Length
1.397(2)
1.369(3)
1.325(3)
1.446(3)
1.369(3)
1.378(3)
0.93
Bond
Length
S(1)—C(7)
O(1)—C(1)
C(3)—C(4)
C(3)—H(3)
C(4)—C(5)
C(5)—C(6)
C(5)—H(5)
C(6)—H(6)
1.380(3)
0.93
N(1)—C(7)
O(2)—C(8)
N(1)—C(4)
O(3)—C(8)
1.384(3)
1.385(3)
0.93
N(1)—H(1)
O(3)—C(9)
N(2)—C(8)
1.375(3)
1.385(3)
0.86
C(1)—C(6)
N(2)—C(7)
C(1)—C(2)
0.93
N(2)—H(2)
C(2)—C(3)
Bond
Angle
129.47
115.3
Bond
Angle
119.8
Bond
Angle
C(7)-N(1)-C(4)
C(7)-N(1)-H(1)
C(4)-N(1)-H(1)
C(8)-N(2)-C(7)
C(8)-N(2)-H(2)
C(7)-N(2)-H(2)
C(1)-O(1)-C(1)
C(8)-O(3)-0C(9)
C(8)-N(2)-C(7)
C(6)-C(1)-O(1)
C(2)-C(1)-O(1)
C(1)-C(2)-C(3
C(1)-C(2)-H(2A)
C(3)-C(2)-H(2A)
C(4)-C(3)-C(2)
C(4)-C(3)-H(3)
C(2)-C(3)-H(3)
C(3)-C(4)-C(5)
C(3)-C(4)-N(1)
C(5)-C(4)-N(1)
C(4)-C(5)-C(6)
C(4)-C(5)-H(5)
C(6)-C(5)-H(5)
C(1)-C(6)-H(6)
C(5)-C(6)-H(6)
N(1)-C(7)-N(2)
N(1)-C(7)-S(1)
O(3)-C(8)-N(2)
O(2)-C(8)-O(3)
O(2)-C(8)-N(2)
N(2)-C(7)-S(1)
119.8
120.1
120.1
115.3
120.1
120.1
128.09
116
120
114.82(19)
126.97(17)
109.02
120.0(2)
120
116
117.6
119.43
124.44
116.13
120.4
125.6(2)
125.4(2)
118.02
116.28
128.09(19)
118.14
121.2
119.8
Chin. J. Chem. 2010, 28, 1902— 1906
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1903

Zhang et al.
FULL PAPER
Table 3 Selected torsion angles (°) for the title compound
Bond
Bond
Angle/(°)
－1.9(4)
173.9(2)
－0.4(4)
Angle/(°)
130.2(2)
－54.04(17)
1.6(3)
C(1)-O(1)-C(1)-C(6)
C(1)-O(1)-C(1)-C(2)
C(6)-C(1)-C(2)-C(3)
O(1)-C(1)-C(2)-C(3)
C(1)-C(2)-C(3)-C(4)
C(2)-C(3)-C(4)-C(5)
C(2)-C(3)-C(4)-N(1)
C(7)-N(1)-C(4)-C(3)
C(7)-N(1)-C(4)-C(5)
C(3)-C(4)-C(5)-C(6)
N(1)-C(4)-C(5)-C(6)
C(2)-C(1)-C(6)-C(5)
O(1)-C(1)-C(6)-C(5)
C(4)-C(5)-C(6)-C(1)
C(4)-N(1)-C(7)-N(2)
C(4)-N(1)-C(7)-S(1)
C(8)-N(2)-C(7)-N(1)
C(8)-N(2)-C(7)-S(1)
C(9)-O(3)-C(8)-O(2)
C(9)-O(3)-C(8)-N(2)
C(7)-N(2)-C(8)-O(2)
C(7)-N(2)-C(8)-O(3)
－174.0(2)
－169.96(19)
1.1(3)
9.0(3)
－3.4(3)
177.83(19)
－33.1(4)
148.1(2)
3.1(3)
9.5(3)
－169.52(18)
3.7(4)
176.99(18)
－6.0(4)
173.3(2)
－178.0(2)
a Symmetry transformation: a: －x＋2, b: －y, c:－z＋1.
Table 4 Hydrogen bonds of the title compounda
π-π stacking interactions between the aromatic rings
with the top and bottom being folded mutually. The
H-bond and π-π stacking interactions in the title com-
pound lead to a three-dimensional structure of the space
(Figure 2). Multiple hydrogen bonds can reduce the en-
ergy. It is good for accumulating of compounds in the
unit. Intermolecular hydrogen bonds between the mole-
cule makes the structure with multi-dimensional net-
work as shown in Figure 2.
D—H…A
d(D—H) d(H…A) d(D…A) ∠(DHA)
N(1)—H(1)…O(2) 0.860
N(2)—H(2)…S(1) 0.860
1.988
2.534
2.668
3.386
135.29
171.01
a Symmetry transformation: －x＋2, －y, －z＋1.
Determination of the specific heat capacity
Using a continuous specific heat capacity mode of
Micro-DSC apparatus, it can be seen that specific heat
capacity of compound presents a good linear relation-
ship with temperature in determining temperature range.
Specific heat capacity equation is shown as Figure 3.
Determination results of the continuous specific heat
capacity of the compounds:
Figure 1 Molecular structure of the title compound.
1
1
C /(J•mol－ •K－ ) 4.7409 102 5.8337T 2.6864
＝
×
－
＋
p
10－ T2 5.4777 10－ T3 4.1750 10－ T4
2
5
8
×
－
×
＋
×
(283.3 K
T
353 K)
≤ ≤
Figure 2 Packing structure along b axis.
The title compound consists of one diphenyl ether,
two thioureido groups and two methoxy-formyl groups.
From Tables 2 and 3, it can be seen that S(1)—C(7)
bond distance is 0.1663 nm between single and double
of C—S, and C(7) is connected to two other atoms N(1),
N(2). The N(1)—C(7) and N(2)—(7) bond length is
0.1339 and 0.1385 nm, respectively, which is also be-
tween C, N single-double bond lengths. It can be seen
the S(1), C(7), N(1) and N(2) four atoms form a conju-
gated system, indicating two conjugate-thioureido
groups in the title compounds.
Figure 3 The Cp curve of the title compound.
Modynamic functions of the compounds
According to the heat capacity of title compound
From Figure 2 and Table 4, we can see that there are
1904
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1902— 1906

Thermodynamic Properties of 4,4'-Bis(3-N-methoxyformyl thioureido)-diphenyloxide
with temperature changes in the formula:
1
1
C /(J•mol－ •K－ ) 4.7409 102 5.8337T 2.6864
＝
×
－
＋
p
10－ T2 5.4777 10－ T3 4.1750 10－ T4
2
5
8
×
－
×
＋
×
(283.3 K
T
353 K)
≤ ≤
accordance with heat capacity and thermodynamic
function relationships,
T
HT－H298.15
＝
CpdT
∫
298.15
Figure 4 Determination results of the continuous.
T
ST－S298.15
＝
Cp/TdT
∫
298.15
mal decomposition of the title compound as amino-
phenyl thiourea (H2NCSNHPH), CH3OH and CO2.
This can be demonstrated in the FTIR spectra of the
residues got 203.51 ℃, there is no characteristic band
T
T
GT－G298.15
＝
CpdT－T
Cp/TdT
∫
∫
298.15
298.15
－
－
1
1
of C＝O (1700 cm ) and C-O-C (1000 cm ). The loss
weight is 31.89% (calcd 30.88%). We assign them to be
CH3OH and CO2. The composition of final residue can
also be demonstrated by the FTIR spectra. The bands at
At 283—343 K temperature region, calculated HT—
H298.15, ST—S298.15, and GT—G298.15, value, is listed in
Table 5
3426 cm－ are the characteristic bands of N—H and
1
1127 cm－ 1 are the characteristic bands of C＝S.
Therefore, the decomposition mechanism of the title
compound is predicted that:
Table 5 Themodynamic functions of the title compound
(HT－ H298.15)/
(ST－ S298.15)/
(GT－ G298.15)/
(kJ•mol )
T/K
－
－
－
－
1
1
1
1
(kJ•mol )
(J•mol •k )
283
288
293
298
303
308
313
318
323
328
333
338
343
－
－
－
－
6.04418
4.04719
2.06232
0.06054
－
－
－
－
20.8051
13.8101
6.97734
0.2031
－
－
－
－
－
－
－
－
－
－
－
－
－
0.15633
0.06988
0.01796
1.5E－ 05
0.01594
0.06589
0.15011
0.26891
0.42251
0.61102
0.83445
1.09263
1.3853
1.977639
4.06355
6.579479
13.40726
20.29339
27.23314
34.20924
41.19685
48.16815
55.09652
61.96053
6.201719
8.391228
10.62708
12.90155
15.20555
17.52999
19.86716
Conclusion
(1) The new compound 4,4'-bis(3-N-methoxyformyl
thioureido)-diphenyloxide was synthesized and its
structure was determined by single-crystal X-ray dif-
fraction.
(2) The specific heat capacity was determined with
Micro-DSC method. Formula of Cp is:
1
Cp/(J•mol － 1•K －
)
4.7409
102
5.8337T
＝
×
－
＋
2.6864 10－ T2 5.4777 10－ T3 4.1750 10－
2
5
8
Thermal behavior decomposition reaction of the
compound
×
－
×
＋
×
T4 (283.3 K
T
353 K)
≤ ≤
Typical DSC and TG-DTG curves for the title com-
pound are shown in Figure 4. The DSC curve indicates
that the thermal decomposition of the title compound
begin at 190.99 ℃ and reach the peak at 198.74 ℃.
The TG-DTG curves show the stage of mass loss proc-
ess. The stage begins at about 190.99 ℃ and completes
at 203.51 ℃ with a mass loss of 31.89%.
(3) The thermal behavior of the title compound un-
der the non-isothermal condition by DSC, TG/DTG
methods was studied.
(4) The specific heat capacity and the thermal be-
havior of the title compound proved that the title com-
pound has good thermal stability, which is benefit to
storage and transport at room temperature.
Heat decomposition mechanism
The TG-DTG curves show the stage of mass loss
process. The stage begins at about 190.99 ℃ and com-
pletes at 203.51 ℃ with the largest weight loss rate.
From the curve, the mass loss is 31.89%, residue weight
is 68.11%, and the process can be assigned to the ther-
References
1
Huang, Z. Z.; Wu, X. L.; Liu, Y. Chin. J. Org. Chem. 1998,
18, 481 (in Chinese).
2
Madan, V. K; Taneja, A. D. J. Indian Chem. Soc. 1991, 68,
Chin. J. Chem. 2010, 28, 1902— 1906
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1905

Zhang et al.
FULL PAPER
162.
89, 74.
3
4
5
6
7
Tobe, Y.; Sasaki, S.-I.; Mizuno, M.; Hirose, K.; Naemura, K.
J. Org. Chem. 1998, 63, 7481.
Raposo, C.; Almaraz, M.; Martin, M. Chem. Lett. 1995, 24,
759.
Xue, S.-J.; Duan, L.-P.; Ke, S.-Y. Chin. J. Struct. Chem.
2004, 23, 441 (in Chinese).
Wenger, P.; Hans, R.; Franke, H. EP190611, 1986, 214—
215, 218 [Chem. Abstr. 105, 221039h].
8
9
El Aamrani, F. Z.; Kumar, A.; Cortian, J. L. Anal. Chem.
Acta 1999, 382, 205.
Schuster, M.; Fresenius, J. Anal. Chem. 1992, 342, 791.
10 Naumov, A. V.; Semenov, V. N.; Lukin, A. N. Inorg. Mater.
2002, 38, 271.
11 Guillon, E.; Mohamadou, A.; Dechamps-Olivier, I.; Barbier,
J.-P. Polyhedron 1996, 15, 947.
12 Zhang, P. J.; Huang, J.; Song, J. R.; Song, Y.; Xu, H. X.
Chem. Commun. 2009 (in Chinese).
Campo, R.; Criado, J. J.; Garcia, E. J. Inorg. Biochem. 2002,
(E1003221 Ding, W.; Lu, Y.)
1906
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1902— 1906