Supramolecular assembly of double-stranded chains, helical chains and catenane-like layers with flexible ligands

Article abstract of DOI:10.1002/zaac.200700577

Four new transition metal coordination polymers, [Co(bpndc)(phen)(H ₂O)]_n (1), [Co₃(bpndc)₃(2,2′- bpy)₂]_n·0.5n(i-C₃H₇OH) (2), and [M(bpndc)(2,2′-bpy)₂]_n (M = Zn, 3; Cu, 4; H ₂bpndc = benzophenone -4,4′-dicarboxylic acid; phen = 1,10-phenanthroline; 2,2′-bpy = 2,2′-bipyridine) have been synthesized by the hydrothermal reactions and characterized by single crystal X-ray diffraction, elemental analysis, and IR spectrum. Because of the introduction of different terminal auxiliary ligands, bpndc ligands in complexes 1 and 2 adopt different coordination modes. In complex 1, bpndc ligands act as tridentate ligand and bridge Co^II ions into 1D double-stranded chains; while complex 2 possesses 2D (4,4) grids, where bpndc ligands adopt tetradente and pentadentate modes. Two such grids interpenetrate to form a novel catenane-like layer. Complexes 3 and 4 are isostructural. Bpndc ligands adopt tetradentate mode and bridge metal ions forming 1D helical chains.

Full text of DOI:10.1002/zaac.200700577

DOI: 10.1002/zaac.200700577
Supramolecular Assembly of Double-Stranded Chains, Helical Chains and
Catenane-like Layers with Flexible Ligands
Chang-Yan Suna,*, Xin-Xin Lib, Shui-Feng Wangb, Wen-Jun Lia, and Xiang-Jun Zhengc,*
Beijing / P. R. China, a Department of Chemistry, University of Science and Technology Beijing, b Analytical and Testing Center, and
c School of Chemistry, Beijing Normal University
Received September 26th, 2007; accepted December 17th, 2007.
Abstract. Four new transition metal coordination polymers,
[Co(bpndc)(phen)(H2O)]n (1), [Co3(bpndc)3(2,2Ј-bpy)2]n ·
bridge CoII ions into 1D double-stranded chains; while complex 2
possesses 2D (4,4) grids, where bpndc ligands adopt tetradente and
pentadentate modes. Two such grids interpenetrate to form a novel
catenane-like layer. Complexes 3 and 4 are isostructural. Bpndc
ligands adopt tetradentate mode and bridge metal ions forming 1D
helical chains.
0.5n(i-C3H7OH) (2), and [M(bpndc)(2,2Ј-bpy)2]n (M ϭ Zn, 3;
Cu, 4; H2bpndc ϭ benzophenone -4,4Ј-dicarboxylic acid; phen ϭ
1,10-phenanthroline; 2,2Ј-bpy ϭ 2,2Ј-bipyridine) have been synthe-
sized by the hydrothermal reactions and characterized by single
crystal X-ray diffraction, elemental analysis, and IR spectrum. Be-
cause of the introduction of different terminal auxiliary ligands,
bpndc ligands in complexes 1 and 2 adopt different coordination
modes. In complex 1, bpndc ligands act as tridentate ligand and
Keywords: Cobalt; Zinc; Copper; Benzophenone-4,4Ј-dicarboxylic
acid; Flexible ligands; Catenane-like layers; Helical chains
Introduction
The design and assembly of coordination polymers is still
attractive, not only due to the fascinating structures, but
also their potential applications in the areas of catalysis,
magnetism, adsorption, and separation [1Ϫ8]. Transition
metal ions, for their low coordination number and stable
coordination geometry, have been extensively used to con-
struct coordination polymers with interesting structures
and desirable properties [9Ϫ15].
It is evident that ligands not only function in balancing
the charge in coordination polymers, but also play an im-
portant role in deriving structural diversity. Long flexible
ligands are excellent structure directing ligands because of
their flexible bridging capability, and usually lead to large
voids, which may further result in interpenetrated or en-
tangled structures [16Ϫ20]. Benzophenone-4,4Ј-dicar-
boxylic acid (H2bpndc) is a typical long flexible ligand. Al-
though there are only a few reports about its coordination
chemistry [21Ϫ24], it can coordinate metal ions with triden-
tate, tetradentate and hexadentate modes. The typical coor-
dination modes are summarized in Scheme 1(aϪe). It’s said
that the introduction of auxiliary ligands will effect the con-
struction of coordination polymers. Bridging auxiliary li-
gands often extend the structures, while terminal auxiliary
ligands usually result in lower-dimensional structures. In
Scheme 1 The coordination modes of bpndc ligands.
this work, we selected H2bpndc to react with CoII ions, and
introduced terminal ligands 1,10-phenanthroline (phen)
and 2,2Ј-bipyridine (2,2Ј-bpy) to the system, respectively. In
order to determine the effect of metal ions on the construction
of coordination polymers, ZnII and CuII ions were introduced,
too. Four new coordination polymers [Co(bpndc)(phen)-
(H2O)]n (1), [Co3(bpndc)3 (2,2Ј-bpy)2]n·0.5n(i-C3H7OH) (2),
and [M(bpndc)(2,2Ј-bpy)2]n (M ϭ Zn, 3; Cu, 4) were ob-
tained. Their synthesis and structures will be reported in
this paper.
Experimental Section
Materials and equipment
* Dr. Chang-Yan Sun
All reagents were used as received without further purification. The
C, H, N microanalyses were carried out with a Vario EL elemental
analyzer. The IR spectra were recorded with a Nicolet Avatar 360
FT-IR spectrometer using the KBr pellet technique. Thermogravi-
Department of Chemistry
University of Science and Technology Beijing
Beijing, 100083, P. R. China
E-mail: scysun@gmail.com
950
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 634, 950Ϫ955

Double-Stranded Chains, Helical Chains and Catenane-like Layers with Flexible Ligands
metric analyses were conducted on a ZRY-2P Thermal Analyzer
using a heating rate of 10 °C/min from room temperature to
900 °C.
[Cu(bpndc)(2,2Ј-bpy)2]n (4). The synthesis of complex 4 followed the
similar procedure for complex 2 except using Cu(Ac)2 ·H2O instead
of CoCl2 ·6H2O. Yield: 0.022 g (45.1 %). Anal. Calcd for
C25H16N2O5Cu (%): C, 61.48; H, 3.28; N, 5.74; found (%): C, 61.04;
H, 3.59; N, 5.58. IR data (KBr pellet, cmϪ1): 3429(m), 3067(m),
1657(s), 1593(s), 1549(s), 1499(m), 1450(m), 1384(s), 1306(m),
1274(m), 1165(w), 1129(w), 1099(w), 1034(w), 934(m), 845(s),
771(s), 737(s).
Synthesis of the complexes
[Co(bpndc)(phen)(H2O)]n (1). A mixture of H2bpndc (0.027 g,
0.1 mmol), CoCl2 ·6H2O (0.024 g, 0.1 mmol), phen·H2O (0.020 g,
0.1 mmol), triethylamine (Et3N, 0.028 ml), isopropanol (5 mL) and
deionized water (5 mL) was sealed in a Teflon-lined stainless vessel
(25 mL) and heated at 140 °C for 72 h under autogenous pressure.
The vessel was then cooled slowly to room temperature. Dark red
single crystals were obtained by filtration, washed with isopro-
panol, and dried in air. Yield: 0.022 g (41.9 %). Anal. Calcd for
C27H18N2O6Co (%): C, 61.69; H, 3.43; N, 5.33; found (%): C, 61.54;
H, 3.51; N, 5.22. IR data (KBr pellet, cmϪ1): 3350(m), 3071(w),
1654(m), 1600(s), 1547(m), 1519(w), 1430(w), 1386(s), 1336(m),
1304(m), 1275(s), 1127(w), 933(m), 849(m), 812(m), 735(s).
X-ray diffraction determination
Diffraction intensities for the four complexes were collected at
293K on a Bruker SMART 1000 CCD area detector diffractometer
employing graphite monochromatized MoKα radiation (λ ϭ
˚
0.71073 A) in φ and ω scan modes. Semi-empirical absorption
correction was applied using the SADABS program [25]. The struc-
tures were solved by direct methods [26] and refined by full-matrix
least squares method on ΗFΗ2 using SHELXS 97 and SHELXL 97
programs, respectively [26, 27]. Non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were placed in geometrically cal-
culated positions. The crystallographic data for the four complexes
[Co3(bpndc)3(2,2Ј-bpy)2]n ·0.5n(i-C3H7OH) (2).
A
mixture of
H2bpndc (0.027 g, 0.1 mmol), CoCl2 ·6H2O (0.024 g, 0.1 mmol),
2,2Ј-bpy (0.016 g, 0.1 mmol), NaOH aqueous solution (0.3 ml,
0.65 mol LϪ1), isopropanol (5 mL) and deionized water (5 mL) was
sealed in a Teflon-lined stainless vessel (25 mL) and heated at
180 °C for 72 h under autogenous pressure. The vessel was then
cooled slowly to room temperature. Dark red single crystals were
obtained by filtration, washed with isopropanol, and dried in air.
Yield: 0.017 g (38.5 %). Anal. Calcd for C66.50H44N4O15.50Co3 (%):
C, 60.28; H, 3.32; N, 4.23; found (%): C, 60.62; H, 3.41; N, 4.26.
IR data (KBr pellet, cmϪ1): 3453(s), 1663(m), 1646(m), 1608(s),
1553(m), 1536(w), 1443(m), 1393(s), 1305(w), 1278(m), 934(w),
837(w), 769(m), 738(m).
˚
are listed in Table 1, and selected bond lengths/A and bond angles/°
in Tables 2 and 3.
Results and Discussion
Description of the structures
In complexes 1-4, bpndc ligands adopt tridentate, tetraden-
tate, and pentadentate coordination modes, as shown in
Scheme 1a, c, f and g. Complexes 3 and 4 are isostructural,
so only the structures of complexes 1-3 will be described
in detail.
Structural description of [Co(bpndc)(phen)(H2O)]n (1).
The coordination environment of CoII ion in complex 1 is
shown in Figure 1. Each CoII is six-coordinated to three
oxygen atoms of three bpndc ligands, one oxygen atom of
one coordinated water molecule, and two nitrogen atoms of
one phen ligand. The coordination can be described as
[Zn(bpndc)(2,2Ј-bpy)2]n (3). The synthesis of complex 3 followed the
similar procedure for complex 2 except that Zn(Ac)2 ·2H2O was
used instead of CoCl2 ·6H2O and the temperature was 140 °C.
Yield: 0.034g (69.4 %). Anal. Calcd for C25H16N2O5Zn (%): C,
61.25; H, 3.27; N, 5.72; found (%): C, 60.97; H, 3.43; N, 5.57. IR
data (KBr pellet, cmϪ1): 3449(m), 3074(m), 1660(s), 1591(s),
1542(s), 1506(m), 1448(m), 1413(s), 1309(m), 1273(m), 1164(w),
1097(w), 1028(m), 933(m), 853(s), 759(s), 735(s).
Table 1 Crystal data and structure refinement parameters for complexes 1Ϫ4
1
2
3
4
Chemical Formula
Formula weight
Crystal system
Space group
C27H18N2O6Co
525.36
C66.50H44N4O15.50Co3
1323.84
monoclinic
C2/c
15.424(2)
16.664(2)
C25H16N2O5Zn
489.77
monoclinic
P21/c
12.508(2)
15.142(2)
11.464(2)
C25H16N2O5Cu
487.94
monoclinic
P21/c
12.730(4)
14.872(5)
11.539(4)
triclinic
¯
P1
˚
a/A
7.736(3)
11.519(4)
13.543(5)
83.152(7)
83.910(7)
71.006(6)
1130.0(8)
2
˚
b/A
˚
c/A
23.997(3)
α/°
β/°
γ/°
97.477(2)
93.421(2)
95.077(5)
3
˚
V/A
6115.3(1)
4
2167.4(5)
4
2175.9(1)
4
Z
F(000)
538
1.544
0.808
293(2)
2702
1.437
0.877
293(2)
1000
1.501
1.174
293(2)
996
1.489
1.044
293(2)
Dc/mg mϪ3
μ, mmϪ1
T/K
θ range/°
GOF
1.52 to 26.40
1.084
1.71 to 26.36
1.056
1.63 to 26.44
1.069
2.11 to 26.42
1.029
Final R indices
[I>2σ(I)]
R1ϭ0.0542,
wR2ϭ0.1153
R1ϭ0.0451,
wR2ϭ0.1411
R1ϭ0.0396,
wR2ϭ0.0761
R1ϭ0.0400,
wR2ϭ0.0835
Z. Anorg. Allg. Chem. 2008, 950Ϫ955
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
951

C.-Y. Sun, X.-X. Li, S.-F. Wang, W.-J. Li, X.-J. Zheng
˚
˚
Table 2 Selected bond lengths/A and angles/° for complexes 1
Table 3 Selected bond lengths/A and angles/° for complexes 3
and 2
and 4
a)
c)
1
3
Co(1)-O(1)
Co(1)-O(4)#1
Co(1)-O(4)#2
2.047(3)
2.101(3)
2.123(3)
Co(1)-N(1)
Co(1)-N(2)
Co(1)-O(6)
O(4)#2-Co(1)-N(1)
O(6)-Co(1)-O(4)#1
O(6)-Co(1)-O(4)#2
O(6)-Co(1)-N(1)
O(6)-Co(1)-N(2)
N(2)-Co(1)-O(4)#2
N(2)-Co(1)-N(1)
2.145(3)
2.108(3)
2.081(3)
168.32(11)
165.34(11)
88.52(11)
101.51(12)
90.22(12)
96.70(11)
77.48(12)
Zn(1)-O(1)
Zn(1)-O(2)
Zn(1)-O(4)#1
O(1)-Zn(1)-O(2)
O(1)-Zn(1)-O(4)#1 101.45(8)
O(1)-Zn(1)-O(5)#1 152.48(9)
O(1)-Zn(1)-N(1)
O(1)-Zn(1)-N(2)
O(2)-Zn(1)-O(4)#1
O(2)-Zn(1)-O(5)#1
O(2)-Zn(1)-N(1)
2.085(2)
2.239(2)
2.127(2)
60.68(8)
Zn(1)-O(5)#1
2.224(2)
2.092(2)
2.075(2)
94.50(9)
60.46(8)
93.42(8)
92.44(9)
92.81(9)
151.33(8)
78.74(9)
Zn(1)-N(1)
Zn(1)-N(2)
O(1)-Co(1)-O(4)#1
O(1)-Co(1)-O(4)#2
O(1)-Co(1)-O(6)
O(1)-Co(1)-N(1)
O(1)-Co(1)-N(2)
O(4)#1-Co(1)-O(4)#2
O(4)#1-Co(1)-N(1)
O(4)#1-Co(1)-N(2)
90.44(11)
97.74(11)
87.95(11)
88.68(12)
165.39(12)
77.26(10)
93.02(11)
94.89(11)
O(2)-Zn(1)-N(2)
O(5)#1-Zn(1)-O(4)#1
O(5)#1-Zn(1)-N(1)
O(5)#1-Zn(1)-N(2)
N(1)-Zn(1)-O(4)#1
N(2)-Zn(1)-O(4)#1
N(2)-Zn(1)-N(1)
108.93(9)
107.21(9)
98.89(8)
99.56(8)
165.65(8)
b)
c)
2
4
Co(1)-O(1)
2.021(2)
2.143(2)
2.188(3)
2.024(3)
2.090(3)
Co(2)-O(2)
2.118(2)
2.118(2)
2.175(2)
2.175(2)
2.128(3)
2.128(3)
180.0
94.12(10)
85.88(10)
85.88(10)
94.12(10)
180.0
86.06(10)
93.94(10)
88.25(10)
91.76(10)
93.94(10)
86.06(10)
91.75(10)
88.24(10)
Cu(1)-O(1)
Cu(1)-O(2)
Cu(1)-O(4)#1
O(1)-Cu(1)-O(2)
O(1)-Cu(1)-O(4)#1 157.50(8)
O(1)-Cu(1)-O(5)#1 105.36(9)
O(1)-Cu(1)-N(1)
O(2)-Cu(1)-O(5)#1
O(2)-Cu(1)-N(1)
O(2)-Cu(1)-N(2)
2.464(2)
1.976(2)
2.409(2)
58.51(8)
Cu(1)-O(5)#1
1.988(2)
1.991(2)
1.991(2)
58.75(8)
96.35(9)
162.89(9)
99.91(9)
81.39(9)
91.75(9)
104.75(9)
Co(1)-O(4)#1
Co(2)-O(2)#2
Cu(1)-N(1)
Co(1)-O(5)#1
Co(2)-O(4)#1
Cu(1)-N(2)
Co(1)-O(6)
Co(2)-O(4)#3
O(5)#1-Cu(1)-O(4)#1
O(5)#1-Cu(1)-N(1)
O(5)#1-Cu(1)-N(2)
N(1)-Cu(1)-O(4)#1
N(1)-Cu(1)-N(2)
N(2)-Cu(1)-O(1)
N(2)-Cu(1)-O(4)#1
Co(1)-N(1)
Co(1)-N(2)
Co(2)-O(7)
2.128(3)
Co(2)-O(7)#2
O(1)-Co(1)-O(6)
O(1)-Co(1)-N(1)
O(6)-Co(1)-N(1)
O(1)-Co(1)-N(2)
O(6)-Co(1)-N(2)
N(1)-Co(1)-N(2)
O(1)-Co(1)-O(4)#1
O(6)-Co(1)-O(4)#1
N(1)-Co(1)-O(4)#1
N(2)-Co(1)-O(4)#1
O(1)-Co(1)-O(5)#1
O(6)-Co(1)-O(5)#1
N(1)-Co(1)-O(5)#1
N(2)-Co(1)-O(5)#1
O(4)#1-Co(1)-O(5)#1
91.42(11)
95.27(12)
90.60(12)
172.49(13)
88.46(13)
77.22(13)
94.84(10)
101.78(10)
163.79(11)
92.53(12)
89.80(11)
162.53(11)
106.63(11)
92.57(12)
60.76(10)
O(2)-Co(2)-O(2)#2
O(2)-Co(2)-O(7)
O(2)#2-Co(2)-O(7)
O(2)-Co(2)-O(7)#2
O(2)#2-Co(2)-O(7)#2
O(7)-Co(2)-O(7)#2
O(2)-Co(2)-O(4)#3
O(2)#2-Co(2)-O(4)#3
O(7)-Co(2)-O(4)#3
O(7)#2-Co(2)-O(4)#3
O(2)-Co(2)-O(4)#1
O(2)#2-Co(2)-O(4)#1
O(7)-Co(2)-O(4)#1
O(7)#2-Co(2)-O(4)#1
108.93(9)
96.54(9)
154.95(9)
92.19(9)
O(2)-Cu(1)-O(4)#1 105.15(9)
c) Symmetry transformations used to generate equivalent atoms:
#1 xϪ1,Ϫyϩ1/2,zϪ1/2
CoII ions, a rhombic Co2O2 core is formed, in which the
Co···Co distance is 3.300 A. These Co2O2 cores are linked
by bpndc ligands to form 1D double-stranded chains, as
shown in Figure 2a. There are hydrogen bonds between the
coordinated water molecules and uncoordinated car-
˚
O(4)#3-Co(2)-O(4)#1 180.0
Symmetry transformations used to generate equivalent atoms:
#1 xϪ1/2,Ϫyϩ1/2,zϪ1/2 #2 Ϫxϩ3/2,Ϫyϩ1/2,Ϫzϩ1 #3 Ϫxϩ2,y,Ϫzϩ3/2
˚
boxylate oxygen atoms (the O···O distance is 2.742 A),
which results in the formation of 2D layers (see Figure 2b).
Structural description of [Co3(bpndc)3(2,2Ј-bpy)2]n ·
0.5n(i-C3H7OH) (2). There are two kinds of crystallograph-
ically independent CoII ions in complex 2, as shown in Fig-
ure 3. Although both Co(1) and Co(2) are six-coordinated
and their coordination can be described as distorted octa-
hedral, their coordination environments are different. Co(1)
is surrounded by four oxygen atoms of three bpndc ligands
a) Symmetry transformations used to generate equivalent atoms: #1 x,y,zϩ1
#2 Ϫx,Ϫyϩ1,Ϫz;
b) Symmetry transformations used to generate equivalent atoms: #1 xϪ1/2,
Ϫyϩ1/2,zϪ1/2 #2 Ϫxϩ3/2,Ϫyϩ1/2,Ϫzϩ1 #3 Ϫxϩ2,y,Ϫzϩ3/2.
distorted octahedral. In complex 1, bpndc ligand adopts a
tridentate mode (see Scheme 1a), bridging three CoII ions.
Because one carboxylate oxygen atom of bpndc bridges two
Figure 1 The coordination environment of CoII ion in complex 1 with 30 % thermal ellipsoids, all hydrogen atoms are omitted for clarity.
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Double-Stranded Chains, Helical Chains and Catenane-like Layers with Flexible Ligands
Figure 4 The representation of 2D catenane-like layer in com-
plex 2 (The ball represents the trinuclear building block, and the
line represents bpndc ligand).
building blocks are linked by bpndc ligands to form a 2D
(4, 4) grid. It’s interesting that in this grid one side is con-
nected by tetradentate bpndc ligand, and the other is
double-connected by two pentadentate bpndc ligands.
Noticeably, two such (4,4) grids interpenetrate each other
to generate a novel 2D catenane-like layer, as shown in Fig-
ure 4. The layers are stacked parallel resulting in the forma-
tion of a 3D supramolecular network. There are cavities
between the layers, at which free isopropanol molecules
are located.
Figure 2 (a) The simple representation of 1D double-stranded
chain constructed by bpndc ligands linking Co2O2 cores in complex
1; (b) The 2D layers formed by 1D chains via hydrogen bonds
viewed along the b axis (the dotted lines represent hydrogen bonds).
Structural description of [Zn(bpndc)(2,2Ј-bpy)2]n (3). The
coordination environment of ZnII ion in complex 3 is shown
in Figure 5. Each ZnII ion is six-coordinated, in which four
oxygen atoms come from two bpndc ligands, and two nitro-
gen atoms come from one 2,2Ј-bpy ligand. In complex 3,
bpndc ligand adopts a new tetradentate mode (see Scheme
1g), and ZnII ions are bridged by bpndc ligands forming a
1D infinite helical chain, as shown in Figure 6a. There are
π-π stacking interactions between the helical chains (the
2,2Ј-bpy ligands are parallel and the face-to-face distance is
and two nitrogen atoms of one 2,2Ј-bpy ligand, while Co(2)
is coordinated to six oxygen atoms of six bpndc ligands.
Co(1) and Co(2) are bridged by three carboxylate groups
˚
with the distance of 3.466 A. Co(2) is in a symmetrical
center. So the trinuclear Co(1)Co(2)Co(1B) shown in Fig-
ure 3 can be regarded as the second building block. In com-
plex 2, bpndc ligands adopt two kinds of coordination
modes, tetradentate and pentadentate (see Scheme 1c and
f). The later has not been reported before. The trinuclear
˚
3.51 A), resulting in the formation of a 3D supramolecular
network (see Figure 6b).
Figure 3 The coordination environment of CoII ions in complex 2 with 30 % thermal ellipsoids, all hydrogen atoms are omitted for clarity.
www.zaac.wiley-vch.de 953
Z. Anorg. Allg. Chem. 2008, 950Ϫ955
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

C.-Y. Sun, X.-X. Li, S.-F. Wang, W.-J. Li, X.-J. Zheng
Figure 5 The coordination environment of ZnII ion in complex 3 with 30 % thermal ellipsoids, all hydrogen atoms are omitted for clarity.
(1), [Co3(bpndc)3(2,2Ј-bpy)2]n ·0.5n(i-C3H7OH) (2), and
[M(bpndc)(2,2Ј-bpy)2]n (M ϭ Zn, 3; Cu, 4). Complex 1 is
of 1D double-stranded chains, while complex 2 possesses
2D catenane-like layers, which is contributed to the intro-
duction of different auxiliary terminal ligands phen and
2,2Ј-bpy. Complexes 3 and 4 are isostructural. Bpndc li-
gands bridge metal ions forming 1D helical chains. The
π-π stacking interactions result in the construction of 3D
supramolecular networks.
Supplementary Data. Crystallographic data for the structural
analysis have been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 661654-661657 for 1Ϫ4 respectively.
Copies of this information may be obtained free of charge
from the CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
Figure 6 (a) The 1D helical chain in complex 3; (b) The 3D supra-
molecular structure of complex 3 viewed along the a axis (Every
helical chain is represented by one colour).
ϩ44-1223-336-033;
e-mail:
deposit@ccdc.cam.ac.uk
or
www:http://www.ccdc.cam.ac.uk).
Acknowledgements. This project is supported by National Nature
Science Foundation of China (20331010, 20501003) and University
of Science and Technology Beijing (00009093).
Thermogravimetric analyses
Complexes 1-4 are very stable in air at ambient temperature
and almost insoluble in common solvents such as water,
alcohol, and acetone. In order to examine their thermal sta-
bility, we carried out thermal gravimetric analyses (TGA)
of complexes 1 and 2. The result shows that complex 1 is
stable up to 208 °C. A weight loss of 3.5 % occurred in the
temperature of 208Ϫ265 °C corresponds to the loss of the
one coordinated water molecule in complex 1 (calc. 3.4 %).
While for complex 2, the first weight loss of 2.0 % from 46
to 60 °C corresponds to the loss of free isopropanol mol-
ecule (calc. 2.3 %). The low decomposition temperature of
complex 2 is consistent with the structure since there are no
hydrogen bonds between the free isopropanol molecule and
the framework. The further decomposition took place at
340 °C and 320 °C for complexes 1 and 2, respectively,
giving the powder of CoO.
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