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Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
SUPPLEMENTARY DATA
A novel porous 3D network [Cu2(glutarate)4(4,4’-bipyridine)]·3H2O:
Single-crystal-to-single-crystal reversible dehydration
Beth Rather and Michael J. Zaworotko *
Department of Chemistry, University of South Florida, 4202 E Fowler Ave (SCA 400), Tampa, FL,
33620, USA.
Materials and Methods
Thermogravimetric analysis was performed under nitrogen (except for the
rehydration of 1a powder and crystals) on TA Instruments TGA 2950 Hi-Res. XRPD
data were recorded on a Rigaku RU15 diffractometer at 30kV, 15mA for CuKα (λ =
1.5418 Å), with a scan speed of 1°/min and a step size of 0.02° in 2θ at room
temperature. The simulated XRPD patterns were produced using Powder Cell for
Windows Version 2.3. For guest readsorption experiments, the concentration changes
were measured by GC using toluene as the internal standard. The data were fitted to
the equation previously published by K. S. Min and M. P. Suh, Chem. Eur. J., 2001,
7, 303.
Table of contents
Figure S1. Conformational analysis of crystal structures containing the glutarate
fragment and metals.
Figure S2. FT-IR spectra of 1a and 1b.
Figure S3. FT-IR spectra of compound 1b let in atmosphere for 55min (from t = 0 to
t = 55min top to bottom).
Figure S4. FT-IR spectra of compound 1b let in MeOH (HPLC grade H2O =
0.009%) for 1 night.
Figure S5. FT-IR spectra of 2a, 2b and 2c.
Figure S6. FT-IR spectra of 2a let in atmosphere for 45min (t=0 to t=45min from top
to bottom)
Figure S7. X-ray powder diffraction patterns of 1a (a) fresh sample, (b) calculated
from the single crystal structure.
Figure S8. X-ray powder diffraction patterns of 1b (a) sample heated to 150ºC, (b)
calculated from the single crystal structure.
Figure S9. X-ray powder diffraction patterns of 2a (a) fresh sample, (b) calculated
from the single crystal structure.
Figure S10. X-ray powder diffraction patterns of (a) blue powder formed during the
synthesis
of
1a
and
(b)
simulation
from
the
structure
of
[Co(4,4’-
bipyridine)1.5(NO3)2]n (CSD code REJVUX).
Figure S11. X-ray powder diffraction patterns of (a) blue crystals formed during the
synthesis of 2a and (b) simulation from the structure of bilayer [Co(4,4’bipyridine)1.5(NO3)2]n (CSD code NAMSEZ).
Figure S12. TGA trace of 1a.
Figure S13. TGA traces of 1a (a) and 1b let in atmosphere for <1hour (b).
Figure S14. TGA traces of the rehydration of 1b powder (a) and 1b crystals (b)
under ambient atmosphere.
Figure S15. TGA traces of 2a, 2b and 2c.
Figure S16. Inclusion of apohost solid 1b with various guests from GC experiments.
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
CSD Refcode
C1-C4
MIYMOW
65
ZADJUJ
69
MEZSALa
69
XATNIPa
69.5
TODNAB
70
QANKOF
43
VIRYUQ
46
GLUECU
59
QIVHAE
62
MASXINa
62
ACBRUA
65
GLTECU
68
SIFWEJ
68
SUJXEA
68
HOTGOM
71
QIWKEM
71
TODNEF
74
QANKIZ disordered 60-66
OCENUF
166
MASXINb
169
XEDCUE
169
QIVGUX
172
TEGMIB
172
VIRZAX
173
CDGLTR
173
MIYMUC
175
FUMCUL
177
HOTHAZ
179
XATNIPb
179
MEZSALb
180
BOMXOQ
Torsion Angles
C2-C5
O1-C3
75
17.5
70
32
69
4.5
69.5
4
77
20
180
95
172
66.5
170
77.6
165
6
180
23
178
26.5
177
19.5
177
43.5
178
21.5
170
0.8
179
8
172
6.5
150-163
3-9
179
51
174
17
176
88
172
7
173
10
173
34.5
175
4.8
176
0.5
180
3.2
179
11
179
10
180
10
no structure
O5-C3
43.5
82.5
4.5
4
7
35
85.4
31.5
77
70.5
87.5
27
54
48
75
49
49.5
30-77
34.5
21
88
7
15.5
95
0.35
32
0.3
8
10
10
Conformation
Gauche-Gauche
Gauche-Anti
Anti-Anti
Figure S1. Conformational analysis of crystal structures containing the glutarate
fragment and metals.
Compound 1a
Compound 1b
Figure S2. FT-IR spectra of 1a and 1b.
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
Figure S3. FT-IR spectra of compound 1b let in atmosphere for 55min (from t = 0 to
t = 55min top to bottom).
Figure S4. FT-IR spectra of compound 1b let in MeOH (HPLC grade H2O =
0.009%) for 1 night.
Compound 2a
Compound 2b
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
Compound 2c
Figure S5. FT-IR spectra of 2a, 2b and 2c.
Figure S6. FT-IR spectra of 2a let in atmosphere for 45min (t=0 to t=45min from top
to bottom)
a
b
Figure S7. X-ray powder diffraction patterns of 1a (a) fresh sample, (b) calculated
from the single crystal structure.
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
a
b
Figure S8. X-ray powder diffraction patterns of 1b (a) sample heated to 150ºC, (b)
calculated from the single crystal structure.
5
10
15
19.52
20
25
25.30
30
36.89
37.36
32.95
36.54
37.05
33.46
33.97
34.43
34.89
35.31
35.83
32.57
31.39
31.96
30.69
29.61
30.10
28.84
28.15
27.31
26.62
29.24
24.10
24.59
25.92
16.31
22.32
22.68
23.13 23.20
21.67
20.57
19.98
18.43
0
16.66
14.61
15.41
25.01
12.8912.88
12.74
7.29
213
13.56
7.69
a
er352
107
35
b
Figure S9. X-ray powder diffraction patterns of 2a (a) fresh sample, (b) calculated
from the single crystal structure.
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
a
17.06
5
10
15
25
30
35.60
34.06
34.52
36.38
36.87
37.39
37.85
35.96
31.45
31.97
32.44
32.90
33.46
29.77
30.00 30.09
30.23
30.66
31.16
29.14
27.28 27.15
26.81
27.91
26.20
25.40
23.99
24.81
21.94
20
22.92
23.45 23.57
20.53
19.74
18.51
16.40
16.84
0
15.19
9.93
9.22
19.93
23.76
25.09
85
17.78
17.58
REJVUXEtOH
11.72
170
35
b
Figure S10. X-ray powder diffraction patterns of (a) blue powder formed during the
synthesis of 1a and (b) simulation from the structure of [Co(4,4’bipyridine)1.5(NO3)2]n (CSD code REJVUX).
8.88
5
10
17.49
13.84
15
20
25
30
35
37.32
37.94
38.24
38.82
39.34
37.07
36.46
35.76
34.89
35.15
34.25
37.50
30.09
30.35
30.67
31.20
31.45
31.88
32.36
32.85
33.36
26.46
25.13
23.06
26.84
27.58
28.13
28.68
29.27
26.03
25.43
23.22
23.77
24.33
21.72
20.39
17.24
25.01
20.82
21.42
16.72
11.55
14.71
13.53
11.82
10.67
26.2826.34
21.15
63
22.08
22.64
19.81
18.43
16.32
15.36
14.37
0
11.27
21.04
125
10.51
6.90
a
NAMSEZ
40
b
Figure S11. X-ray powder diffraction patterns of (a) blue crystals formed during the
synthesis of 2a and (b) simulation from the structure of bilayer [Co(4,4’bipyridine)1.5(NO3)2]n (CSD code NAMSEZ).
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
Figure S12. TGA trace of 1a.
a
b
Figure S13. TGA traces of 1a (a) and 1b let in atmosphere for <1hour (b).
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
a
b
Figure S14. TGA traces of the rehydration of 1b powder (a) and 1b crystals (b)
under ambient atmosphere.
a
b
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
c
Figure S15. TGA traces of 2a, 2b and 2c.
Guest G
MeOH
EtOH
CH3CN
n-hexane
Guest (mol) included per
unit formula of 1b
5.00.10-9
3.94.10-7
6.70.10-7
1.21.10-8
Figure S16. Inclusion of apohost solid 1b with various guests from GC experiments.