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Y. Zhu et al. / Journal of Solid State Chemistry 219 (2014) 259–264
and catalytic properties. To date, research on the properties of
complexes with H3TTTA and the similar ligands are mainly focused
on the luminescence and magnetism and so on. There are few
reports about molecular and cationic recognition as well as
catalytic properties of these compounds.
Table 1
Crystal data and structure refinements for La-TTTA and Nd-TTTA.
Compound
La-TTTA
Nd-TTTA
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C18H20La2N6O20S6
1110.58
193
C9H10N3NdO10S3
560.62
193
Monoclinic
P21/c
Triclinic
2. Experimental
P1
a (Å)
b (Å)
c (Å)
α (1)
8.9930(18)
13.214(3)
14.518(3)
86.89(3)
87.01(3)
86.08(3)
2.149
8.7281(17)
14.495(3)
15.445(5)
90.00
121.07(2)
90.00
2.225
4
1,092
6,903
2578
3.535
1.086
0.1414
0.3259
0.1459
0.3278
2.1. Materials and physical methods
The ligand was prepared according to the previous procedure
[12]. All other reagents were commercially available and used as
purchased. The elemental analyses were carried out with a Perkin-
Elmer 240 elemental analyzer. The FT-IR spectra were recorded
from KBr pellets in the range of 400–4000 cmꢁ1 on a Nicolet
spectrometer. Thermal analyses were performed on integrated
thermal STA 449C analyzers from room temperature to 800 1C
with a heating rate of 10 1C/min under flowing nitrogen. The
fluorescence spectra of compounds in different solvents and
solutions were performed on a QuantaMaster TM 40 & Time-
Master spectrophotometer. Powder X-ray diffraction (PXRD)
patterns were collected on a Rigaku D/max2500VB3þ/PC diffract-
ometer equipped with Cu-Kα radiation (λ¼1.5406 Å).
β (1)
γ (1)
Dc (g/cm3)
Z
2
F (0 0 0)
1,080
14,845
4560
2.910
0.931
0.0714
0.1890
0.0887
0.2057
Reflections collected
Unique reflections
μ (mmꢁ1)
Goodness-of-fit on F2
R1 [I42σ(I)]
wR2 [I42σ(I)]
R1 (all data)
wR2 (all data)
ultrasound for 2 h in the sealed vial. After the reaction completed,
the catalyst was removed by centrifugation and then filtered with
ethyl acetate quickly. The conversion of aldehydes was determined
by gas chromatography (GC, Agilent 7890 A) analysis and GC–MS
(HP 6890) spectra with those of authentic samples.
2.2. Synthesis of La-TTTA
A mixture containing H3TTTA (0.035 g, 0.1 mmol) and La
(NO3)3 ꢀ 6H2O (0.086 g, 0.2 mmol) in 3 mL water was sealed in a
Teflon-lined autoclave and heated to 80 1C under autogenous
pressure for two days and then allowed to cool to room tempera-
ture. After filtration, the white block crystals were washed with
water and dried in air. Anal. Calcd for C18H20La2N6O20S6 (Mr:
1110.58): C, 19.47; H, 1.82; N, 7.57%. Found: C, 19.08; H, 1.89; N,
7.51%. IR (cmꢁ1): 3426(m), 1582(s), 1479(s), 1419(s), 1385(s), 1269
(w), 1226(m), 848(w).
3. Results and discussion
3.1. Synthetic and spectral aspects
The two compounds were characterized by powder XRD, TG
analysis, and FT-IR spectroscopy. The experimental powder XRD
patterns were measured at room temperature as shown in Fig. S1.
The peak positions of the simulated and experimental PXRD
patterns are in agreement with each other, suggesting the good
phase purity of the two compounds. TG analysis revealed that all
these materials have good thermal stabilities, since they start to
decompose beyond 300 1C (Figs. S2 and S3).
2.3. Synthesis of Nd-TTTA
Nd-TTTA was obtained in a similar manner to La-TTTA using Nd
(NO3)3 ꢀ 6H2O (0.086 g, 0.2 mmol). After filtration, the crystals
were washed with water and dried in air. Anal. Calcd for
C9H10NdN3O10S3 (Mr: 560.62): C, 19.28; H, 1.80; N, 7.50%. Found:
C, 19.13; H, 1.92; N, 7.43%. IR (cmꢁ1): 3424(m), 1580(s), 1474(s),
1418(s), 1384(s), 1270(w), 1224(m), 848(w).
The characteristic absorption peaks of the main functional
groups in FT-IR spectra for all the compounds are shown in Fig.
S4. The asymmetric stretching vibrations υas(COOꢁ) of the two
compounds were observed in about 1582, 1580, 1597 cmꢁ1 and
2.4. Crystal structure determination and refinement
symmetric stretching vibrations υs(COOꢁ
)
in 1385, 1384,
1403 cmꢁ1. The difference Δ(υas(COOꢁ)ꢁυs(COOꢁ)) was about
The X-ray intensity data for the two compounds were collected
on a Rigaku Saturn 724þCCD diffractometer with graphite mono-
chromatized Mo Kα radiation (λ¼0.71073 Å). The crystal structures
were solved by direct methods using difference Fourier synthesis
with SHELXTS [13], and refined by full-matrix least-squares
method using the SHELXL-97 program [14]. The non-hydrogen
atoms were refined with anisotropic displacement parameters.
Hydrogen atoms except for those of guest molecules were added
according to theoretical models. Crystal data and details of the
structure determination for La-TTTA and Nd-TTTA are listed in
Table 1. Selected bond lengths and angles for La-TTTA and Nd-
TTTA are listed in Table S1.
200 cmꢁ1, characteristic for coordinated carboxylate groups [15].
3.2. Crystal structural description of La-TTTA and Nd-TTTA
Single-crystal X-ray analyses indicate that the only small
difference between La-TTTA and Nd-TTTA is the coordination
mode of La1 metal center. The bond length of La1–O3 is 2.896
(7) Å, which is a little longer than the common La–O bond lengths.
However, regarding La1–O3 as a weak coordination bond, La-TTTA
and Nd-TTTA are isostructural. Herein, the structures and proper-
ties of La-TTTA are described in detail as a representative example.
La-TTTA crystallizes in the triclinic space group P1. The ORTEP
view of La-TTTA is shown in Fig. 1. La ion is ten-coordinated by
five TTTA3ꢁ ligands and two water molecules to finish distorted
monocapped square anti-prism coordination geometry. The La–O
(carboxylate) bond distances vary from 2.473(7) to 2.896(7) Å, and
the average La–O (water) bond distance is 2.566(7) Å. The O–La–O
2.5. Catalytic test for cyanosylation reaction
Aldehyde (1.0 mmol) in trimethylsilyl cyanide (TMSCN,
2 mmol) was successively placed into a 10 mL screw-cap vial and
compound (2.5 mol%) was then added to initiate the reaction with