Inorganic Chemistry
Article
Two sites are located by N1/C5 and N2/C6 atoms in two pydc
ligands with 50% occupancies due to the symmetrical feature. All H
atoms on water molecules were directly included in the molecular
formula. A summary of crystal data and structure refinements for
compound FeW−PYDC is provided in Table 4.
4.4. Procedure for the Selective Oxidation of Alkanes. In a
typical operation, alkanes (1 mmol), a powdered catalyst (0.3 mol %),
a solvent (0.5 mL), and TBHP (70% aqueous solution, 3 mmol) were
added successively to a tube at room temperature. The mixture was
further placed on a parallel reactor and stirred for a certain time under
preset conditions. The product was qualitatively detected by GC−MS,
and the yield of the product was monitored by GC using naphthylene
as the internal standard. At the end of each cycle, the catalyst was
recovered by centrifugation after the reaction mixture was cooled to
room temperature and then washed thoroughly (at least three times)
with benzonitrile and dried in an oven at 100 °C overnight to be
reused for the recyclability experiments.
Table 4. Crystal Data and Structural Refinement of FeW−
PYDC
empirical formula
formula weight
crystal system
space group
a (Å)
b (Å)
c (Å)
α (deg)
β (deg)
C21Fe4N3O59PW12
3698.81
triclinic
P1
̅
12.8533(5)
13.1878(6)
13.3075(5)
115.3610(10)
108.8460(10)
98.9700(10)
1811.24(13)
1
γ (deg)
volume (Å3)
Z
ρcalc (g/cm3)
3.391
μ (mm−1
F(000)
)
19.864
1626.0
0.16 × 0.14 × 0.12
5.376−50.198
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
■
crystal size (mm3)
sı
2θ range for data collection
(deg)
index ranges
−15 ≤ h ≤ 15, −15 ≤ k ≤ 15,
−15 ≤ l ≤ 14
21824
6419 (Rint = 0.0518; Rσ = 0.0516)
6419/211/460
1.036
BVS, IR, selected bond lengths and angles, and
additional catalytic properties of FeW−PYDC (PDF)
no. of reflections collected
no. of independent reflections
data/restraints/parameters
goodness of fit on F2
Accession Codes
CCDC 2015761 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
a
b
R1, wR2 [I ≥ 2σ(I)]
R1 = 0.0763, wR2 = 0.1543
R1 = 0.0985, wR2 = 0.1673
a
b
R1, wR2 (all data)
a
b
R1 = ∑||Fo| − |Fc||/∑|Fo|. wR2 = [∑w(Fo2 − Fc2)2/∑w(Fo )2]1/2; w
2
= 1/[σ2(Fo ) + (xP)2 + yP], where P = (Fo + 2Fc2)/3, where x =
2
2
0.0396 and y = 112.8222 for FeW−PYDC.
AUTHOR INFORMATION
Corresponding Authors
■
Mettler-Toledo TGA/SDTA 851e instrument heated from 25 to 800
°C at a heating rate of 10 °C min−1, under a dynamic nitrogen
atmosphere. The powder X-ray diffraction (PXRD) patterns were
recorded on a Bruker D8 Advance instrument with Cu Kα radiation
(λ = 1.5418 Å). X-ray photoelectron spectroscopy (XPS) was
performed with an Axis Ultra X-ray photoelectron spectrometer. GC
analyses were performed on a Bruker 450-GC instrument with a flame
ionization detector equipped with a 30 cm column (GsBP-5, 0.25 mm
internal diameter and 0.25 μm film thickness) with nitrogen as the
carrier gas.
4.2. Preparation of FeW−PYDC. FeW−PYDC was prepared
under hydrothermal conditions by the self-assembly approach.
H3PW12O40·15H2O (0.10 mmol, 300 mg), FeCl3·9H2O (2 mmol,
540 mg), and pydc (1 mmol, 167 mg) were dissolved in 10 mL of
distilled water at room temperature. The resulting suspension was
stirred for 60 min, sealed in a 30 mL Teflon-lined reactor, and heated
at 160 °C for 5 days. After slowly cooling to room temperature at a
rate of 10 °C h−1, yellow block crystals of FeW−PYDC were isolated,
collected by being washed three times with distilled water, and then
air-dried to give a yield of 70% (based on W). Elemental analysis (%)
calcd for C21Fe4N3O59PW12 (Mr = 3698.81): Fe, 6.83; P, 0.82; W,
59.61; C, 6.79; N, 1.21. Found: Fe, 6.80; P, 0.84; W, 59.65; C, 6.82;
N, 1.19. IR (KBr, cm−1): 3406 (w), 1604 (s), 1407 (s), 1342 (m),
1072 (s), 962 (s), 887(s), 794 (s) (Figure S1).
4.3. Single-Crystal X-ray Crystallography. A good single
crystal of FeW−PYDC with dimensions of 0.16 mm × 0.14 mm ×
0.12 mm was prudently picked under an optical microscope and
sealed in a glass tube closed at both ends. Intensity data were
collected on a Bruker APEX-II CCD detector at 150 K with Mo Kα
radiation (λ = 0.71073 Å). The structure was determined with olex2.
The structure was determined using charge flipping and refined with
the olex2 refinement package using Gauss−Newton minimization.62,63
Two paris of tungstate atoms (W2 and W2B or W6 and WB) have
thermal parameters similar to the site occupancies of 70% and 30%.
Jingyang Niu − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China;
Jingping Wang − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China;
Authors
Quanzhong Wang − Henan Key Laboratory of
Polyoxometalate Chemistry, College of Chemistry and
Chemical Engineering, Henan University, Kaifeng 475004,
Henan, P. R. China
Baijie Xu − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China
Yingyue Wang − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China
Hui Wang − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China
Xin Hu − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China
Pengtao Ma − Henan Key Laboratory of Polyoxometalate
Chemistry, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng 475004, Henan, P. R. China
7759
Inorg. Chem. 2021, 60, 7753−7761