Synthesis and characterization of antimony trichloride and bismuth trichloride complexes with valine

Article abstract of DOI:10.1007/s10973-008-9045-8

Two compounds of antimony trichloride and bismuth trichloride with valine are synthesized by solid phase synthesis at room temperature. Their compositions, determined by element analysis, are Sb(C₅H ₁₀O₂N)₃?2H

Full text of DOI:10.1007/s10973-008-9045-8

Journal of Thermal Analysis and Calorimetry, Vol. 96 (2009) 1, 277–285
SYNTHESIS AND CHARACTERIZATION OF ANTIMONY TRICHLORIDE
AND BISMUTH TRICHLORIDE COMPLEXES WITH VALINE
J. G. Shao1, Y. X. Yang2*, B. W. Li2, L. P. Zhang2, Y. R. Chen2 and X. L. Liu3
1College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P.R. China
2Department of Chemistry, East China University of Science and Technology, 200237, P.R. China
3Analysis Test Center, Yangzhou University, Yangzhou 225009, P.R. China
Two compounds of antimony trichloride and bismuth trichloride with valine are synthesized by solid phase synthesis at room tem-
perature. Their compositions, determined by element analysis, are Sb(C5H10O2N)3·2H2O and Bi(C5H10O2N)2Cl·0.5H2O. The crystal
structure of antimony complex with valine belongs to triclinic system and its lattice parameters are: a=0.9599 nm, b=1.5068 nm,
c=1.9851 nm, a=92.270, b=95.050, g=104.270. The crystal structure of bismuth complex with valine belongs to monoclinic system
and its lattice parameters are: a=1.6012 nm, b=1.8941 nm, c=1.839 nm, b=99.73°. The far-infrared spectra and infrared spectra
show that the amino group and carboxyl of valine may be coordinated to antimony and bismuth, respectively, in two compounds.
The TG-DSC results also reveal that the complexes were formed.
Keywords: antimony, bismuth, complexes, solid phase reaction, synthesis, trichloride, valine
Introduction
were all of A.R. grade, Shanghai Chemical Reagent
Company Ltd., Shanghai, China).
The complexes of antimony and bismuth have biologi-
cal function, such as anti-cancer, sterilization, and so on
[1–4]. However, the preparation of the solid complexes
of trivalent antimony and bismuth ions is different from
that of the other transition metal ions, as the antimony
and bismuth ions are easily hydrolyzed in the aqueous
solution [5]. The synthesis of the solid complexes of the
antimony and bismuth ions by a general solution reac-
tion is very difficult and few complexes of antimony and
bismuth are reported. Recently, many transition metal
complexes have been obtained by solid phase synthesis
[6], but few complexes of antimony and bismuth by
solid phase synthesis are reported. In this paper, two
complexes of antimony and bismuth with valine are
synthesized by solid phase method, and the complexes
are characterized by several analytical methods, such as
element analysis, X-ray diffraction, far-infrared spectra
and TG-DSC.
Synthesis of lithium valine salt
8.7863 g (75 mmol) valine, 40 mL deionized water
and 3.147 g (75 mmol) LiOH·H2O were put into the
three necked bottle. The mixture was stirred for 4 h at
30°C until the solution was clear. The solvent was
rotoray evaporated, filtrated and dried in the vacuum
for 1 h. Finally lithium valine salt was obtained.
Synthesis of complex of valine with antimony
1.1075 g (9 mmol) lithium valine and 0.6840 g (3 mmol)
antimony trichloride were mixed well together. The
mixture was carefully ground in an agate mortar for
30 min and several drops of acetonitrile were added as
initiator. At first, the mixture became slightly viscous,
indicating that the reaction did happen. Soon after that,
the mixture became powdery. One continued grinding
for 8 h. The product was dried in the vacuum at 80°C for
4 h and then washed with anhydrous methanol until no
chloride ion was found in the washing solution. The ob-
tained powder was next dried in the vacuum at 80°C and
finally a new complex of valine with antimony
trichloride was obtained.
Experimental
Materials
Reagent
Valine as ligand, lithium hydroxide (LiOH·H2O) as
alkali to prepare lithium valine salt, antimony
trichloride (SbCl3), and bismuth trichoride (BiCl3)
can offer positively charged central metal ion Sb3+ or
Bi3+ in following preparation, (the above reagents
Synthesis of complex of valine with bismuth
1.1089 g (9 mmol) lithium valine and 0.9395 g (3 mmol)
bismuth trichoride were mixed well together. The mix-
*
Author for correspondence: yuxyang@online.sh.cn
1388–6150/$20.00
Akadémiai Kiadó, Budapest, Hungary
Springer, Dordrecht, The Netherlands
© 2009 Akadémiai Kiadó, Budapest

SHAO et al.
ture was carefully ground in an agate mortar for 30 min
To check whether the new complex contain chloride
ions, the synthesized complex was dissolved with
concentrated nitric acid. When the AgNO3 was added
into the solution, no precipitates were found, which
show the new complex does not contain chloride ions,
further demonstrate the above molecular formula.
The relative content of the element in complex of
bismuth valine: C (theor. 24.72%; found 25.05%),
H (theor. 4.33%; found 4.61%), N (theor. 5.77%;
found 5.68%) and Bi (theor. 43.00%; found 43.71%),
respectively. The element analyses yield the composi-
tion Bi(C5H10O2N)2Cl·0.5H2O of the complex. In the
molecular formula, 0.5 mol H2O is considered as ad-
sorbed water. To verify whether the complex of
valine with bismuth contain chloride ions, the com-
plex was dissolved by concentrated nitric acid, no
sooner the AgNO3 was added into the solution, then
the solution began to precipitate, the results show
complex contain chloride ions, further demonstrate
the above molecular formula.
and several drops of acetonitrile were added as initiator.
At first, the mixture became slightly viscous, indicating
that the reaction did happen. Soon after that, the mixture
became powdery. One continued grinding for 8 h. The
product was dried in the vacuum at 80°C for 4 h and
then washed with anhydrous methanol until no chloride
ion was found in the washing solution. The obtained
powder was next dried in the vacuum at 80°C and fi-
nally a new complex of valine with bismuth trichloride
was obtained.
Instrumental methods
Carbon, hydrogen and nitrogen in the complexes
were determined by an Elementar Vario EL element
analysis. The content of antimony and bismuth in the
resultant were measured by TJA IRIS1000 type
ICP-AES analysis.
The powder X-ray diffraction patterns of the prod-
ucts, recorded by a Rigaku D/max-2550VB/PC X-ray
diffractometer, using CuK radiation, scanning rate
a1
XRD analysis and discussions of complex for
antimony valine, bismuth valine
2° (2q) min–1 at room temperature, are presented in
Fig. 1. The results of indexing of the X-ray diffraction
patterns are listed in Tables 1–3. The far-infrared and in-
frared spectra of the complexes were measured by a
Nicolet 5D-FT spectrometer, using the cesium iodide
disk technique. The far-infrared measurements of the
standard valine and of the complexes with valine in the
range from 50 to 650 cm–1 are presented in Figs 2–4,
while the infrared spectra of the three complexes in the
range from 400 to 4000 cm–1 are shown in Fig. 5.
The thermal decomposition process of the resul-
tant was studied by a JETZSCH-STA-449C differen-
tial thermal balance in nitrogen using platonic cruci-
bles, with a heating rate of 10°C min–1 and a-Al2O3
reference. The possible pyrolysis reactions, experi-
mental and calculated percentage mass losses in the
thermal decomposition process for the complexes,
which resulted from thermogravimetric and differen-
tial thermal analysis curves of the complexes are sum-
marized in Tables 4 and 5.
The X-ray diffraction patterns of the resultants are re-
corded and shown in Fig. 1. The X-ray diffraction pat-
terns of valine and its complexes all display sharp
peak with strong diffraction intensity, and low back-
ground. The crystal spacing dexp and relative intensity
(I/I0) of the antimony valine, bismuth valine com-
plexes are completely different from diffraction of
ligand valine, and standard diffraction card JCPDS
1-248(SbCl3), JCPDS 43-756(BiCl3) of the reactants,
which demonstrates the reactants have formed new
compounds and are not the simple mixtures of metal
chlorides with ligand valine.
From the powder X-ray diffraction pattern of the
complex bismuth valine shown in Fig. 1, we can also
Results and discussions
Element analysis of the compounds
The element analyses indicate that the relative con-
tent of the element in complex of antimony valine:
C (theor. 35.57%; found 35.03%), H (theor. 6.72%;
found 6.56%), N (theor. 8.30%; found 7.99%) and
Sb (theor. 24.11%; found 24.74%), respectively. The
element
analyses
yield
the
composition
Sb(C5H10O2N)3·2H2O of the complex. In the molecu-
lar formula, a H2O is considered as adsorbed water.
Fig. 1 X-ray patterns of lithium valine, antimony valine and
bismuth valine
278
J. Therm. Anal. Cal., 96, 2009

ANTIMONY TRICHLORIDE AND BISMUTH
found that the diffraction peaks are considerably wid-
The results of indexing to the powder X-ray dif-
fraction pattern are listed in Tables 1–3.
ened, perhaps which reveals the solid complex bis-
muth valine maybe is nanoparticles. From the widen-
ing of the diffraction peaks, we can approximately
evaluate the average size of the resultant particles by
Scherrer formula. The calculations indicate that the
particles of the solid complex are in the nano range
and their average size may be less than 100 nm.
Tables 1–3 show that all the diffraction peaks in
the pattern of lithium valine and the complexes anti-
mony valine, bismuth valine can be readily indexed
by a set of lattice parameters. The largest relative de-
viation between the calculated and experimental is
less than 0.37%, which indicates that all the three
products of the reaction are single phase compounds,
Table 1 The experimental data and the calculated results for powder X-ray diffraction pattern of the lithium valine, monoclinic
symmetry: a=1.5024 nm, b=2.0651 nm, c=2.7963 nm, b=100.73°
2q
D
D0
h k l
I/%
2q
D
D0
h k l
I/%
6.240
7.299
14.153
12.101
6.045
5.063
4.875
4.647
4.52
14.1478
12.0981
6.049
1 0–1
1 0 1
2 0 2
2 3–1
1 4 0
2 3–3
1 1–6
2 3–4
2 4–2
3 2 2
3 3–4
0 0 8
1 0 8
3.4
100
20.3
29.560
30.481
31.640
32.420
33.380
35.301
36.040
37.180
39.860
42.020
44.960
48.720
3.019
2.93
3.0199
2.9309
2.8228
2.7596
2.6828
2.5395
2.4885
2.4164
2.2594
2.1454
2.0129
1.8668
0 1 9
1 5 6
3 0 7
2–6 4
2 3 8
1 8–1
2 6 6
0 8–4
5–6–1
2 9 2
1 8 8
6 7 1
22.6
1.5
3.4
1.0
1.0
1.5
1.0
2.6
1.1
0.6
0.4
0.4
14.640
17.499
18.180
19.081
19.620
20.421
21.299
22.060
23.999
25.922
27.727
2.825
2.759
2.682
2.54
5.067
5.1
2.5
3.4
3.5
2.1
4.4
3.2
2.9
0.7
0.3
4.8733
4.6688
4.5121
4.331
2.49
4.345
4.168
4.026
3.704
3.434
3.214
2.416
2.259
2.148
2.014
1.867
4.1702
4.0327
3.7117
3.4343
3.2154
Table 2 The experimental data and the calculated results for powder X-ray diffraction pattern of the antimony valine, triclinic
symmetry: a=0.9599 nm, b=1.5068 nm, c=1.9851 nm, a=92.27°, b=95.05°, g=104.27°
2q
D
D0
h k l
I/%
61.3
2q
D
D0
h k l
I/%
7.301
13.700
14.641
18.319
19.140
19.641
20.500
22.060
23.720
24.101
25.000
26.001
27.641
28.626
29.561
32.021
32.520
33.460
34.981
12.096
6.434
6.048
4.829
4.628
4.548
4.320
4.024
3.750
3.688
3.559
3.433
3.218
3.114
3.018
2.793
2.753
2.676
2.562
12.098
6.458
6.045
4.838
4.633
4.516
4.328
4.026
3.747
3.689
3.558
3.424
3.224
3.115
3.019
2.792
2.751
2.675
2.562
0 1–1
1 0 2
35.984
37.182
37.820
39.539
39.920
42.002
45.078
45.960
48.201
54.480
57.100
59.060
64.079
67.000
68.760
73.921
67.220
77.920
2.495
2.419
2.377
2.277
2.258
2.147
2.011
1.975
1.887
1.682
1.609
1.561
1.452
1.393
1.366
1.283
1.249
1.225
2.493
2.416
2.376
2.277
2.256
2.149
2.009
1.973
1.886
1.682
1.611
1.562
1.452
1.395
1.364
1.281
1.248
1.225
1–4 6
0 5–5
2 4–4
0–5–5
0–3 8
4–3 3
0 7 2
4 2 2
2 6 2
1 7 5
1 7 6
3 7–1
4 6–5
4 6 4
2 7 8
4 8 0
5 5 6
4 6 8
0.7
2.2
1.4
2.0
1.6
3.1
0.6
31.7
1.2
27.8
7.6
4.9
2.6
2.9
2.8
6.5
5.6
1.0
12.5
14.1
5.9
0 2–2
1 0 0
2–3 0
1 0–4
1–3 2
2–1–3
0 1 5
12.2
8.0
5.7
2.8
0.9
1–1–5
2 0–4
1–3–4
1 3–4
3–1–2
2 1–5
3–1–4
3–2 3
1–4–5
2 0 6
3.0
0.4
1.8
100
1.0
18.1
33.6
5.5
2.4
9.2
J. Therm. Anal. Cal., 96, 2009
279

SHAO et al.
Table 3 The experimental data and the calculated results for powder X-ray diffraction pattern of the bismuth valine,
monoclinic symmetry: a=1.6012 nm, b=1.8941 nm, c=1.839 nm, b=99.73°
2q
D
D0
h k l
I/%
2q
D
D0
h k l
I/%
7.280
11.980
14.640
18.320
19.159
19.660
20.480
22.061
24.100
25.900
29.599
32.600
33.440
63.621
12.125
7.389
6.044
4.843
4.625
4.500
4.334
4.020
3.687
3.438
3.012
2.742
2.675
2.452
12.132
7.381
6.045
4.838
4.628
4.511
4.332
4.025
3.689
3.437
3.015
2.744
2.677
2.451
1 1 0
1 2 1
32
37.375
40.960
45.021
46.760
48.480
49.760
54.260
58.700
60.383
68.340
69.565
74.420
77.780
2.404
2.203
2.010
1.940
1.875
1.830
1.689
1.571
1.530
1.371
1.351
1.274
1.231
2.404
2.201
2.011
1.941
1.876
1.830
1.689
1.571
1.531
1.371
1.350
1.273
1.226
–2 0 9
0 6 7
6 4 4
–6 0 9
–3 6 9
3 6 8
8 0 5
5 9 5
8 4 6
9 7 4
8 4 9
7 9 8
7 9 9
0.4
9.4
9.0
–2 2 1
–2 0 4
0 4 1
7
5.2
1.2
31.7
3.5
11.7
7.9
–3 1 3
0 4 2
6.3
4.4
18.4
15.3
1.2
3 2 2
1.2
–4 2 1
–2 1 6
–5 2 2
–2 3 7
4 3 4
3.6
52.5
11.4
100.0
34.5
1.7
7.7
1.0
4.1
8.3
–6 2 4
the crystal structure of lithium valine belongs to
monoclinic system, while the crystal structure of
complexes antimony valine and bismuth valine be-
long to triclinic system and monoclinic system, re-
spectively.
The far infrared spectrum of the compounds
To verify the complex formation between the anti-
mony ion and valine, as well the complex formation
between the bismuth ion and valine for further study-
ing coordination properties of complex, we per-
formed far-IR experiments on the complex within the
range of spectrum 50–650 cm–1. The far-infrared
spectrum of valine, the ligand (lithium salt of valine),
the complexes antimony valine and bismuth valine,
can be seen from Figs 2–5, respectively.
Fig. 2 Far infrared spectrum of standard valine
to there may being only the amino group (–NH2), not
any protonated amino group (–NH+3 ) in the lithium
valine salt. It is also obtained that the spectrum of
COO– vibrations moves to 302.7 and 280.9 cm–1 due
to coordination between COO– and lithium ion.
The far infrared spectrums of two complexes anti-
mony valine, bismuth valine are more complicated than
the far-infrared spectrum of valine. The difference be-
tween Figs 2 and 4 show that the peak at 493.7 cm–1
may be from stretching vibration of Sb–N [8] bond, and
the peak at 379 cm–1 may be from stretching vibration of
Sb–O [8] bond, the existence of the Sb–N and Sb–O ab-
sorption peaks demonstrate the formation of the com-
plex antimony valine. It is also found that the bands near
542.2 cm–1 of the corresponding normal valine shift to
543.1 cm–1, and this phenomenon is also found in far-in-
frared spectrum of bismuth valine, which verifies the
formation of the complex.
As shown in Fig. 2, valine shows seven peaks at
542.2, 471.0, 428.6, 376.7, 337.0, 295.9 and 272.7 cm–1
in the far-IR region, among which the peak at
542.2 cm–1 may be from COO– vibration, a pair of peaks
at 471.0 and 428.6 cm–1 may be from NH3+ torsion-vi-
bration [7]. Because the free amino acid often exists as
an inner salt, there are always both protonated amino
group (–NH+3 ) and deprotonated carboxyl group
(–COO–) in the free amino acid. Besides, a pair of peaks
at 376.7 and 337.0 cm–1 may be from the CCaN defor-
mation vibration, a pair of peaks at 295.9 and
272.7 cm–1 may be from COO– vibrations [7].
The far-infrared spectrum of lithium valine salt
is different from that of valine, as shown in Fig. 3. A
new distinct peak at 614.7 cm–1 may be from COO–
rocking/wagging/bending vibration [7], which might
be coordinated to lithium ion. The spectrum of NH3+
torsion-vibration moves to 479.3 and 419.1 cm–1, due
280
J. Therm. Anal. Cal., 96, 2009

ANTIMONY TRICHLORIDE AND BISMUTH
Fig. 5 Far infrared spectrum of bismuth valine
Fig. 3 Far infrared spectrum of lithium valine
1329 cm–1 are associated with the stretching or shear
deformation vibration of C–H bond in –CH–NH2. It is
also found that the peaks at 1587 and 1397 cm–1 may
be due to the symmetric and asymmetric stretching of
carboxylic group, and the peak at 1508 cm–1 may be
due to the stretching vibration of C–O bond. A weak
broad peak at 3306 cm–1 may be due to stretching vi-
bration of N–H bond. The adsorption peaks at 1329,
1271 and 1034 cm–1 may be due to the symmetric and
asymmetric stretching or deformation vibration of the
N–C bond in the –CH–NH2 group.
For the ligand of lithium valine (Fig. 6), we con-
cluded that the peaks at 2966, 2930 cm–1 may be due to
the symmetric and asymmetric stretching or deforma-
tion vibration of the C–H bond. While the peaks at 3366
and 3285 cm–1 can be assigned to symmetry and asym-
metric stretching vibration of N–H bond. The adsorp-
tion peaks at 1367, 1174 and 1013 cm–1 may be due to
the symmetric and asymmetric stretching or deforma-
tion vibration of the N–C bond in the –CH–NH2 group.
The adsorption peaks at 1855, 1581 and 1397 cm–1 may
be due to the vibrations of carboxylic group.
Fig. 4 Far infrared spectrum of antimony valine
In contrast to Fig. 2, the absorption peak at
475 cm–1 may be from stretching vibration of Bi–N
[8], the absorption peak at 376 cm–1 may be from
stretching vibration of Bi–O [8] in Fig. 5. While the
absorption peak at 77, 63 cm–1 can be assigned to
symmetry and asymmetric stretching vibration of
Bi–Cl bond [9], which indicates the presence of chlo-
ride in complex of bismuth valine.
When the lithium valine was respectively re-
acted with antimony trichloride and bismuth
trichloride to form complexes of antimony valine and
bismuth valine, the characteristic peaks of carboxylic
group either disappear or shift in the spectrum. For
example, the peak at 1581 shift to 1640 cm–1, and the
peak at 1855 cm–1 disappears, but the peak at
1397 cm–1 keeps unchanged. The spectrum of two
complexes also shows that the shift in the spectrum of
characteristic peaks corresponding to the N–C bond
occurs, as can be seen from Fig. 6, the peaks at 1367,
1174 and 1013 cm–1, respectively shift to 1360, 1271
and 1030 cm–1. In the spectrum, the peaks of N–H at
3366 and 3285 cm–1 was disappeared. The intensities
of the peaks are also changed. Especially, some new
peaks were appeared in the spectrum of complex, for
example, the peaks corresponding to the C–H bond in
–CH(CH3)2 and –CH–NH2 appear at 2631 and
2110 cm–1, respectively. These can be attributed to
The infrared spectra of compounds
In order to study coordination properties of the com-
plexes, we also performed the IR experiments on the
ligand (lithium valine) and the complexes for antimony
valine as well as bismuth valine. The following results
can be obtained by comparing the standard spectrum of
coordination ligand and spectrum of complexes.
As shown in Fig. 6, the IR spectrum of valine
displays a distinct peak of hydroxyl group at
3154 cm–1, a distinct peak of H2O at 1587 cm–1, and
three stretching vibrations of C–H bond at 2977, 2947
and 2896 cm–1. Besides, the C–H bond also has two
pairs of peaks, 2627 and 1351 cm–1 are associated
with the stretching or shear deformation vibration of
C–H bond in –CH(CH3)2, whereas 2106 and
J. Therm. Anal. Cal., 96, 2009
281

SHAO et al.
Fig. 7 TG and DSC curves of antimony valine
Fig. 6 Infrared spectra of ligand and synthesized complexes
the complex formation between the antimony ion (or
bismuth ion) and valine.
It is also found that a very broad adsorption peak
at 3400 cm–1 appears in the complex of antimony
valine, and a comparatively broad adsorption peak at
3400 cm–1 appears in the complex of bismuth valine.
This demonstrates that the complex of antimony
valine contains more amount of H2O than the com-
plex of bismuth valine.
Thermal decomposition analysis of the compounds
The TG-DSC was made in order to verify the bonds and
composition of complex. The results are shown in Figs 7
and 8, the data of possible thermal decomposition pro-
cesses are shown in Tables 4 and 5, respectively.
Fig. 8 TG and DSC curves of bismuth valine
case the sample would gradually lose the C2H2NH2,
CO and CO2 with increasing temperature.
Table 4 shows that the first mass loss of the com-
plex Sb(C5H10O2N)3·2H2O begins at about 252°C, the
experimental mass loss (25.36%) indicates the losing of
2H2O and 6CH3 (the calculated percentage mass loss:
24.92%). The elimination of the H2O from the complex
and cleavage of methyl from isopropyl of valine need
certain energy, therefore, there is a considerable endo-
thermic peak at about 252°C in DSC curve.
To check whether the intermediate compound is
(C2O4)SbOSb(C2O4),
a
certain amount (about
100 mg) of complex Sb(C5H10O2N)3·2H2O was
placed in tube type electric-resistance furnace and in
nitrogen at 270°C for several minutes, the IR spec-
trum of cooled sample was observed by
a
Nicolet 5D-FT spectrometer, as can be seen in the fol-
lowing Fig. 9. It is found that the peak of the symmet-
ric and asymmetric stretching or deformation vibra-
tions of the C–H bond almost disappear, the peaks at
1360, 1271 and 1030 cm–1 are also found to disap-
pear, indicating the vibration of the N–C bond in the
–CH–NH2 group has disappeared. The IR spectrum
displays peaks of carboxylic group at 1646.1 (strong)
and 1530.7 cm–1 (medium), whereas a pair of peaks,
735.3 (very strong) and 956.6 cm–1 (medium) are as-
sociated with the Sb–O–Sb bridge [10], which
matches the spectrum of (C2O4)SbOSb(C2O4). The
new strong peak at 3271 cm–1 may be due to the anti-
mony oxalate hydrate, because the intermediate com-
pound (C2O4)SbOSb(C2O4) is easily hydrolyzed by
moist air before observation of IR spectrum.
The second mass loss of the sample occurs at
about 270°C and there is a small exothermic peak in
DTA curve. It is due to the elimination of 3 moles of
C2H2NH2, 0.5 mol CO and 0.5 mol CO2 from the com-
plex. The experimental mass loss (about 31.50%) is
close to the calculated one (32.03%). In the thermal
decomposition process, the reaction of the pyrolysis
products leads to an exothermic peak in DSC curve,
probably because the nitrogen atoms of C2H2NH2 are
not directly coordinated to antimony ion, whereas the
loss of CO and CO2 from the complex indicates car-
bonyl and CO2 cleavage from carboxyl directly coor-
dinated to antimony ion, which lead to more stable in-
termediate compound (C2O4)SbOSb(C2O4). In that
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ANTIMONY TRICHLORIDE AND BISMUTH
Table 4 Thermal decomposition data of complex Sb(C5H10O2N)3·2H2O
Mass loss/%
Reaction
T/°C
Mexp.
Mtheor.
Sb(C5H10NO2)3·2H2O
¯–2H2O; –2·3CH3;
SbC9N3H12O6
252 (endo.)
270 (exo.)
315 (endo.)
460 (endo.)
25.36
31.50
11.14
24.92
32.03
11.06
¯–3C2H2NH2; 1/2CO; 1/2CO2;
1/2{(C2O4)SbOSb(C2O4)}
¯–2CO
1/2(O2SbOSbO2)
¯–1/2O2;
2.87
3.16
1/2Sb2O3
29.13
28.80
Table 5 Thermal decomposition data of complex Bi(C5H10O2N)2Cl·0.5H2O
Mass loss/%
Reaction
T/°C
Mexp.
Mtheor.
Bi(C5H10NO2)2Cl·0.5H2O
¯–(CH3)2CHNH2CHCOO; –0.5H2O
243 (endo.)
26.29
19.00
5.91
25.76
18.97
5.47
0.5[(CH3)2CHNH2CHCOO]Bi(m-Cl2)Bi[OOCHNH2CH(CH3)2]
¯–(CH3)2CHNH2CHC; –0.25O2
0.5OBiO(m-Cl2)BiO
¯–0.375Cl2
300 (endo.)
331 (endo.)
353 (endo.)
0.5OBiO(m-Cl0.5)BiO*
¯–0.125Cl2;
1.46
1.82
0.5Bi2O3
47.34
47.98
*Its structure can be seen in the following:
O–Bi–O–Bi–O
|
Cl
|
O–Bi–O–Bi–O
When the temperature is higher than 315°C, the
sample will lose the residual organic ligands and be-
come Sb2O5. While with temperature increasing over
460°C, the pyrolysis product Sb2O5 will lose the oxy-
gen in nitrogen and become gradually to stable Sb2O3.
Finally the pyrolysis residue is yellow Sb2O3 powder.
Similarly, the solid complex Bi(C5H10O2N)2Cl·
0.5H2O will also lose 0.5 mol water molecule and
1 mole organic ligands (CH3)2CHNH2CHCOO, the ex-
perimental mass loss (about 26.29%) is close to the cal-
culated one (25.76%). The cleavage of ligands
(CH3)2CHNH2CHCOO from the solid complex also
need certain energy, therefore, there is a considerable
endothermic peak at about 243°C in DSC curve. Then,
at 300°C, the sample will cleave (CH3)2CHNH2CHC
and 0.25O2 from (CH3)2CHNH2CHCOO, the elimina-
tion of the (CH3)2CHNH2CHC from the complex need
certain energy, and thus, there is a corresponding endo-
thermic peak in DSC curve.
To check whether the first intermediate com-
pound is
[(CH3)2CHNH2CHCOO]Bi(m-Cl2)Bi[OOCHNH2CH
(CH3)2] and the second intermediate compound is
OBiO(m-Cl2)BiO, two certain amounts (about
100 mg) of complex Bi(C5H10NO2)2Cl·0.5H2O were
placed in tube type electric-resistance furnace and in
nitrogen at 243 and 300°C, respectively for several
minutes, the IR spectrum of cooled samples were ob-
served by a Nicolet 5D-FT spectrometer, as can be
seen in the following Figs 10a and b.
In Fig. 10a, the IR spectrum appears a strong
peak at 471.2 cm–1 due to the Bi–Cl–Bi bridge vibra-
tion [11], and a medium peak at 1628.7 cm–1 due to
carboxylic group vibration. At 1103.7 cm–1 appears a
very strong peak due to the N–C bond in organic
ligand [(CH3)2CHNH2CHCOO], while a medium
peak around 800.0 cm–1 is ascribed to Bi–O–Bi link-
age vibration [12, 13]. This shows the IR spectrum re-
J. Therm. Anal. Cal., 96, 2009
283

SHAO et al.
When temperature is above 331°C, the sample
lose the residual chloride ion, forming the products
OBiO(m-Cl0.5)BiO with the Bi–Cl–Bi bridge, there is
also a corresponding endothermic peak in DSC curve.
The result is in a good agreement with the far infrared
spectrums, further demonstrating the presence of
chloride ligand in complex of bismuth valine. When
the temperature is higher than 353°C, the sample will
lose the residual chloride ions and become Bi2O3, the
experimental percentage mass loss (47.34%) consists
with the calculated that 47.98%. Finally, the residue
is yellow Bi2O3 powder.
The pyrolysis process of the two samples both
shows that the elimination of the nitrogen atoms from
complex occurs at one time, indicating there being
only one kind of nitrogen atoms in the complex. On
the conclusion, it is one nitrogen atom on the amino
group of valine that is coordinated directly to anti-
mony ion or bismuth ion, adsorption peaks of Sb–N
and Bi–N are determined by far-infrared spectrum,
which verify the existence of complex further.
Fig. 9 Infrared spectrum of intermediate compound in Table 4
The thermal decomposition process of the two
samples also shows that the elimination of the oxygen
atoms from complex occurs step by step at two or
three different temperatures, but not at one time. Es-
pecially, the complex of antimony valine firstly loses
CO carbonyl and CO2, but at last loses 0.5O2, indicat-
ing the oxygen atom in the complex is coordinated di-
rectly to the antimony ion in the complex. In compari-
son with antimony valine, the complex of bismuth
valine firstly loses (CH3)2CHNH2CHCOO, secondly
loses 0.25O2, and at last loses chloride ion, also dem-
onstrating the oxygen atom and chloride atom in the
complex are coordinated directly to the bismuth ion in
the complex. The adsorption peaks of Sb–O, Bi–O
and Bi–Cl determined by far-infrared spectrum
certainly verify the existence of complex further.
Fig. 10 Infrared spectrum of intermediate compound in
Table 5, a – Bi(C5H10O2N)2Cl·0.5H2O complex heated
in nitrogen at 243°C, b – Bi(C5H10O2N)2Cl·0.5H2O
complex heated in nitrogen at 300°C
corded in Fig. 10a can match the spectrum of
[(CH3)2CHNH2CHCOO]Bi(m-Cl2)Bi[OOCHNH2CH
(CH3)2].
When the sample was heated in nitrogen at 300°C,
the very strong peak at 1103.7 cm–1 sharply decreases,
and the peak of carboxylic group at 1628.7 cm–1 (me-
dium) is found to be disappeared, indicating the organic
ligand (CH3)2CHNH2CHCOO is almost removed from
the sample. It is also found that the peak of the Bi–Cl–Bi
bridge at 471.2 moves to 528.9 cm–1 with peak intensity
decreasing, and the peak of the Sb–O at 800.0 cm–1
moves to 865.7 cm–1. This shows the IR spectrum re-
corded in Fig. 10b can match the spectrum of
OBiO(m-Cl2)BiO. The results of infrared spectrum fur-
ther demonstrate the thermal decomposition process of
complex Bi(C5H10O2N)2Cl·0.5H2O.
Conclusions
Two complexes of antimony valine, and bismuth
valine can be synthesized by the solid-solid reaction
at room temperature. The crystal structure of anti-
mony valine belongs to triclinic system, its lattice pa-
rameters are: a=0.9599 nm, b=1.5068 nm,
c=1.9851 nm, a=92.270, b=95.050, g=104.270, while
the crystal structure of bismuth valine belongs to
monoclinic system, its lattice parameters are:
a=1.6012 nm, b=1.8941 nm, c=1.839 nm, b=99.73°.
The composition of complex is determined by ele-
mental analysis and ICP-AES analysis, the structure
of complex is characterized by XRD, far-infrared, in-
frared and TG-DSC, which can give the evidence of
complex formation between antimony ion (or bismuth
ion) and coordination ligand. The results also demon-
Figures 10a and b all show a new strong peak at
3426 cm–1, probably because the intermediate com-
pound is easily hydrolyzed by moist air before obser-
vation of IR spectrum.
284
J. Therm. Anal. Cal., 96, 2009

ANTIMONY TRICHLORIDE AND BISMUTH
4 X. Xin, J. Solid State Chem., 132 (1997) 291.
strate that the solid complex bismuth valine is nano-
particles, which has not been ever reported by litera-
ture before. The amino group and carboxy group of
valine are coordinated directly to antimony ion or bis-
muth ion in the two complexes, the evidence of vibra-
tion of Bi–Cl bond in far-infrared spectrum indicates
the chloride is bonded directly to bismuth ion.
5 People’s Republic of China Petroleum and Chemical
Division Department Standards, HG13-1061-77, Chemical
Reagents, Antimony trichloride.
6 G.-Q. Zhong, Appl. Chem. Ind., 31 (2002) 31 (Chinese).
7 Z. Jixin et al., Analytical Chemistry Experiment, East
China of Science and Technology, University Press 1989.
8 Y. C. Guo, S. R. Luan, Y. R. Chen, X. S. Zang, Y. Q. Jia
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Acknowledgements
10 M. J. Taylor, L.-J. Baker, C. E. F. Rickard and
P. W. J. Surman, J. Organomet. Chem., 498 (1995) C14.
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The project was supported by Shanghai Municipal Natural
Science Foundation and was supported by the Open Project
Program of State Key Laboratory of Inorganic Synthesis and
Preparative Chemistry, Jilin University.
12 T. J. Boyle, D. M. Pedrotty, B. Scott and J. W. Ziller,
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