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S1
Supporting Information
A Tetragonal Prismatic {Co32} Nanocage Based on Thiacalixarene
Yanfeng Bi, Shentang Wang, Mei Liu, Shangchao Du, Wuping Liao,*
1. Experimental Section
2. Crystallographic data
3. Scheme of p-tert-butylthiacalix[4]arene
4. Connection mode of the shuttlecock SBU
5. Packing of the nanocages
6. TGA-DSC analyses
7. FT-IR spectra
8. 1H NMR measurement
9. CO2 sorption
10. Selected bond distances and angles
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013
S2
Experimental Section
Materials and Measurements: p-tert-Butyltetrathiacalix[4]arene (H4TC4A) was synthesized by
literature method1 and other reagents were purchased from commercial sources and used as
received. Co, S, and Cl analyses were determined by a HITACHI S-4800 Scanning Electron
Microscope equipped EDS. Elemental analysis for C, H, O was recorded on a VarioEL instrument.
TGA measurement is performed on a NETZSCH STA 449F3. FT-IR spectra (KBr pellets) were
taken on a Bruker Vertex 70 spectrometer. 1H-NMR spectra were recorded on a Bruker AV 400
(DMF-d7 as internal standard, chemical shifts in ppm). Low-pressure gas sorption experiments were
carried out on a Micromeritics ASAP-2020M automatic volumetric instrument. Ultrahigh-purity N2
and CO2 gases were used in adsorption measurements. The N2 and CO2 isotherms were measured
using a liquid nitrogen bath (77 K) and mixted ice-water bath (273K), respectively. Magnetic
susceptibility measurement for CIAC-108 was performed on a Quantum Design MPMS XL-5
SQUID system in the temperature range of 2–300 K. Diamagnetic corrections for the sample and
sample holder were applied to the data.
Synthesis of CIAC-108: Although we did not experience any problems in the present work, azide
complexes are potentially explosive. Only a small amount of material should be prepared and
handled with care. All experiments were performed in an isolated room and guarded with protective
equipments. Red single crystal blocks of CIAC-108 are obtained from the reaction of the mixture of
p-tert-butylthiacalix[4]arene (0.09g, 0.13 mmol), Co(CH3COO)2·4H2O (0.1 g, 0.4 mmol), NaN3
(0.0325g, 0.5 mmol), and 1,3-dicyanobenzene (0.0256 g, 0.2 mmol), CHCl3 (6 ml), and CH3OH
(6ml) in a 20 ml Teflon-lined autoclave which was kept at 130 °C for 3 days and then slowly cooled
to 20 C at about 4 C/h. The crystals were isolated by filtration and then washed with 1:1
methanol-chloroform and dry in air. Yield (0.085g): ca. 56 % with respect to H4TC4A. The EDS
analysis reveals that the molar ratio of Co: S: Cl molar is 10.78: 10.75: 5.65, comparable to the
expected value (32: 32: 16 = 2: 2: 1). Elemental analysis: calculated (%) for C352 Cl16Co32H368
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N56O32S32, C 45.10, H 3.96, N 8.37; found (after dried in vacuum): C 44.30, H 3.81, N 8.58. FT-IR
(cm-1
): 3409(m), 2962(s), 2870 (w), 2147(m), 2083(w), 1593(w), 1479(s), 1445(s), 1395(m),
1362(m), 1301(s), 1260(s), 1089(s), 883(w), 836(s), 742(s), 671(w), 543(w), 498(w), 459(m).
Chloride anions were unexpectedly found in the final products and the assignment was based on
charge balance and the long bond distances (2.61-2.73Å for μ4-Cl-Co and 2.41 Å of μ2-Cl-Co,
longer than a common Co-O distance).2
Characterization: The intensity data were recorded on a Bruker APEX-II CCD system with
Mo-K radiation ( = 0.71073 Å). The crystal structures were solved by means of Direct Methods
and refined employing full-matrix least squares on F2 (SHELXTL-97).
3 Even the low temperature
data set obtained at about 150K for the compound reveals highly disordered solvents within the
lattice interstices. The diffraction data were treated by the “SQUEEZE” method as implemented in
PLATON.4 All the non-hydrogen atoms were refined anisotropically, and hydrogen atoms of the
organic ligands were generated theoretically onto the specific atoms and refined isotropically with
fixed thermal factors. Since the crystals do not diffract very well due to the structure disorder, the R
factors in the final structure refinement are relatively large, but typical in such system.
CCDC-921770 contains the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
The TENTATIVE assignment of the solvents are describled in detail as below:
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.005 -0.007 -0.020 23148 12654 ' '
2 0.500 0.000 0.000 487 49 ' '
3 0.000 0.500 0.500 487 49 ' '
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SQUEEZE analysese estimate the elcetron count to be 12662 within 24122 Å3 void, which are
occupied by solvents (CHCl3 or CH3OH).5 So there are 218 CHCl3 (58 e-) molecules or 703
CH3OH (18 e-) molecules per unit cell and 109 CHCl3 or 352 CH3OH for each formula,
respectively, since Z = 2. The suitable formula for this compound might be
{[CoII
4(TC4A)Cl]8L4(N3)8Cl8}•109 CHCl3 or {[CoII
4(TC4A)Cl]8L4(N3)8Cl8}•352 CH3OH.
[1] N. Iki, C. Kabuto, T. Fukushima, H. Kumagai, H.Takeya, S. Miyanari, T. Miyashi and S.
Miyano, Tetrahedron., 2000, 56, 1437.
[2] Y. F. Bi, G. C. Xu, W. P. Liao, S. C. Du, X.W. Wang, R. P. Deng, H. J. Zhang and S. Gao, Chem.
Commun., 2010, 46, 6362.
[3] G. M. Sheldrick, Acta Crystallogr. Sect. A: Fundam. Crystallogr., 2008, 64, 112.
[4] P. van der Sluis and A. L. Spek, Acta Cryst. Sect. A., 1990, 46, 194.
[5] O. V. Dolomanov, D. B. Cordes, N. R. Champness, A. J. Blake, L. R. Hanton, G. B. Jameson,
M. Schröder and C. Wilson, Chem. Commun., 2004, 642.
Table S1. Crystal data and structure refinement for CIAC-108
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formula C352H368Cl16Co32N56O32S32
formula wt. 9373.90
Cryst. syst orthorhombic
space group Immm
a (Å) 39.7452(14)
b (Å) 31.0576(12)
c (Å) 32.6515(12)
α (° ) 90
β (° ) 90
γ (° ) 90
V ( Å 3
) 40305(3)
Z 2
Dc/g cm-3
0.772
μ/mm-1
0.807
F(000) 9552
Tot. Data 9656
Uniq. Data 6318
Rint 0.1266
GOF 1.052
R1a [I>2σ(I)] 0.0746
wR2b(all data) 0.2316
aR1 = Σ||F0|-|Fc||/Σ|F0|;
bwR2 = {Σ[w(F0
2-Fc
2)2]/Σ[w(F0
2)2]}
1/2
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S6
S S
S S
OH HO
OH
OH
tBu
tBu
tBu
tBu
Scheme S1. H4TC4A
Fig. S1 Coordination of a Co4-TC4A SBU.
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S7
Fig. S2 Molecular structure of nanocage CIAC-108.
Fig. S3 Scheme of the tetragonal arrangement of eight Co4-TC4A SBUs
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S8
Fig. S4 Polyhedral representation (left) and scheme (right) for the metal arrangement. Polyhedrons
are highlighted in four colors for distinguishing those belong to different SBUs. In right, the blue
balls and linkage show the coordination mode of in situ generated ligand L.
Fig. S5 A nanocage with calixarene molecules omitted (left) and a bottom view of a half (right).
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S9
Fig. S6 Depiction of the octahedral supramolecular arrangement of six adjacent nanocages. The
yellow sphere serves to guide the eyes for the hydrophobic void.
0 100 200 300 400 500 600 700 800
20
40
60
80
100
Temperature (oC)
Weig
htl
oss (
%)
-8
-6
-4
-2
0
2
4
Tem
pera
ture
Diffe
ren
ce (
oC)
Fig. S7 TG/DSC curves of CIAC-108 (in air). TG analysis on CIAC-108 indicates that the onset of
the solvent loss is at the very beginning of recording and the weight decreases gradually to 120 °C
corresponding to the release of the solvent CHCl3 and CH3OH molecules. Further weight loss takes
place without showing any distinct plateau before 250°C. And then the compound began to
decompose gradually and reached a stable weight at ca. 800 °C with unidentified decomposition
products.
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S10
4000 3000 2000 1500 1000 50010
20
30
40
50
60
70
80
90
100
459
498543
671
742
803
836
8831203
+
+
+1089
1260
1301
1392
1395
1455
1593
1729
2083
2147
2870
2962
3409
Wavenumber/cm-1
Tra
nsm
itta
nce(%
)
Fig. S8 FT-IR spectra of the title compound.
Fig. S9 1H-NMR spectra of CIAC-108 (DMF-d7, 400 MHz, 313 K).
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013
S11
0 100 200 300 400 500 600 700 800
0
10
20
30
40
50
60
Vab
s(c
m3 g
-1, S
TP
)
P (mmHg)
CO2-absorption
CO2-desorption
Fig. S10 Adsorption (black) and desorption (red) isotherms of CO2 on CIAC-108 (0 oC).
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S12
Table S2 Selected bond distances (Å) and angles (º) for CIAC-108
Co(1)-O(1) 2.026(6) Co(4)-O(3) 2.038(5)
Co(1)-O(4) 1.985(5) Co(4)-O(4) 1.967(5)
Co(1)-S(1) 2.494(3) Co(4)-S(4) 2.491(2)
Co(1)-N(1) 2.118(6) Co(4)-N(4) 2.123(6)
Co(1)-Cl(1) 2.614(2) Co(4)- Cl(1) 2.627(2)
Co(1)- Cl(4) 2.406(2) Co(4)- Cl(3) 2.406(2)
Co(2)-O(1) 2.016(6) Co(3)-O(2) 1.994(6)
Co(2)-O(2) 2.009(5) Co(3)-O(3) 2.005(5)
Co(2)-S(2) 2.476(3) Co(3)-S(3) 2.483(2)
Co(2)-N(2) 2.204(6) Co(3)-N(3) 2.183(6)
Co(2)-N(6) 2.065(10) Co(3)-N(7) 2.035(7)
Co(2)- Cl(1) 2.732(2) Co(3)- Cl(1) 2.706(2)
Co(1)-O(1)-Co(2) 108.5(3) Co(2)-O(2)-Co(3) 114.1(3)
Co(3) -O(3)-Co(4) 108.1(2) Co(4) -O(4)-Co(1) 114.7(2)
Co(1)-Cl(1)-Co(2) 75.7(6) Co(1)-Cl(1)-Co(3) 122.5(7)
Co(1)-Cl(1)-Co(4) 78.9(6) Co(1)-Cl(2)-Co(1)#1 105.2(3)
Co(4)-Cl(3)-Co(4)#2 105.3(4)
#1, 1-x,y,z; #2, x,-y,z.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2013