A Cubic Co32 Nanocage Incorporating Eight Co4-p-tert ...1H-NMR spectra were recorded on a Bruker AV 400 (DMF-d 7 as internal standard, chemical shifts in ppm). Low-pressure gas sorption

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


S3

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 ' '


http://www.ccdc.cam.ac.uk/data_request/cif

S4

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


S5

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


S6

S S

S S

OH HO

OH

OH

tBu

tBu

tBu

tBu

Scheme S1. H4TC4A

Fig. S1 Coordination of a Co4-TC4A SBU.


S7

Fig. S2 Molecular structure of nanocage CIAC-108.

Fig. S3 Scheme of the tetragonal arrangement of eight Co4-TC4A SBUs


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).


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.


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).


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).


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.


Documents

A Cubic Co32 Nanocage Incorporating Eight Co4-p-tert ...1H-NMR spectra were recorded on a Bruker AV 400 (DMF-d 7 as internal standard, chemical shifts in ppm). Low-pressure gas sorption