Syntheses, crystal structures, and properties of three co(II) supramolecules constructed from phenyl imidazole dicarboxylates

Article abstract of DOI:10.1080/15533174.2012.684269

Three mononuclear cobalt(II) complexes, [Co(H₂MOPhIDC) ₂ (H₂O)₂]·2H₂O (H ₃MOPhIDC = 2-(3-methoxyphenyl)-1H-imida-zole-4,5-dicarboxylic acid) (1), [Co(H₂MOPhIDC)₂(H

Full text of DOI:10.1080/15533174.2012.684269

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:1204–1210, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.684269
Syntheses, Crystal Structures, and Properties of Three Co(II)
Supramolecules Constructed From Phenyl Imidazole
Dicarboxylates
Zhifang Xiong,1 Hongliang Jia,2 Bing Ma,1 and Gang Li1
1Department of Chemistry, Zhengzhou University, Zhengzhou, Henan, P. R. China
2Zhengzhou Infant Normal School, Zhengzhou, Henan, P. R. China
generate H2IDC−, HIDC2−, and IDC3− anions at different pH
values and can afford various coordination modes.[11] Our group
now has strong interest in introducing the bulky aromatic group
into the H3IDC compound, and has confirmed that 2-phenyl-1H-
imidazole-4,5-dicarboxylic acid (H3PhIDC) shows strong coor-
dination ability and various coordination modes,[17–19] which
can build up beautiful metal-organic frameworks.
Herein, we continuously adopt the H3PhIDC ligand and
another similar structural ligand, 2-(3-methoxyphenyl)-1H-
imidazole-4,5-dicarboxylic acid (H3MOPhIDC), to synthe-
size desired complexes. In this study, three mononuclear
complexes, namely [Co(H2MOPhIDC)2(H2O)2]·2H2O (1),
[Co(H2MOPhIDC)2(H2O)2]·2CH3CN (2), and [Co(H2PhIDC)2
(H2O)] (3), have been synthesized (Scheme 1). Their thermal
and fluorescence properties have been investigated as well.
Three mononuclear cobalt(II) complexes, [Co(H2MOPhIDC)2
(H2O)2]·2H2O (H3MOPhIDC = 2-(3-methoxyphenyl)-1H-imida-
zole-4,5-dicarboxylic acid) (1), [Co(H2MOPhIDC)2(H2O)2]·
2CH3CN (2), and [Co(H2PhIDC)2(H2O)] (3) (H3PhIDC
=
2-phenyl-1H-imidazole-4,5-dicarboxylic acid), have been hy-
dro(solvo)thermally synthesized by fine control over synthetic
conditions such as solvent, pH value, and temperature. Their
molecular structures have been characterized by IR spectra,
elemental analyses, and thermogravimetric analyses and further
characterized by single-crystal X-ray diffraction. Furthermore,
the photoluminescent properties of the three complexes have been
investigated.
Keywords crystal structure, property, supramolecule, synthesis
INTRODUCTION
Recently, in the field of crystal engineering and supramolec-
ular chemistry, people found that the design and preparation
organic ligands showing various coordination modes at both
molecular and supramolecular levels is of great importance,[1–10]
by which, diversity structural complexes could be explored and
obtained. In this context, heterocyclic carboxylate ligands, for
instance pyridine carboxylate, pyrazole carboxylate, and imi-
dazole carboxylate ligands have attracted much attention due
to their flexible coordination modes and strong coordination
ability.[11–16] Prompted by the intriguing coordination features of
the imidazole dicarboxylate ligand, imidazole-4,5-dicarboxylic
(H3IDC), which is a planar rigid compound and has six potential
donor atoms (two imidazole nitrogen atoms and four carboxy-
late oxygen atoms), can be partially or fully deprotonated to
EXPERIMENTAL
General Details
All chemicals were of reagent-grade quality obtained from
commercial sources and used without further purification. The
organic ligands H3PhIDC and H3MOPhIDC were prepared ac-
cording to the literature method.[20] C, H, and N analyses were
carried out on a FLASH EA 1112 analyzer (USA). IR data
were recorded on a BRUKER TENSOR 27 spectrophotome-
ter (Germany) as KBr pellets in the 400–4000 cm−1 region.
TG measurements were performed by heating the sample from
20–650◦C at a rate of 10◦C·min−1 in air on a Netzsch STA
409PC differential thermal analyzer (Germany). Fluorescence
spectra were characterized at room temperature by a F-4500
fluorescence spectrophotometer (Japan).
Preparation of [Co(H2MOPhIDC)2(H2O)2]·2H2O (1)
A mixture of H3MOPhIDC (52.4 mg, 0.2 mmol),
CoCl2·6H2O (23.8 mg, 0.1 mmol) and deionized water (8 mL)
was sealed in 25 mL Teflon-lined bomb and heated at 160◦C for
4 days. The reaction mixture was then allowed to cool to room
temperature. Pink crystals of 1 were collected, and dried in air.
Yield: 66%. Anal. Calcd. for C24H26N4O14Co (%): C, 44.16; H,
Received 7 March 2012; accepted 8 April 2012.
The authors gratefully acknowledge the financial support by the Na-
tional Natural Science Foundation of China (21071127 and J0830412)
and the Natural Science Foundation of Henan Educational Committee
(2009A150028 and 2011A150029).
Address correspondence to Gang Li, Department of Chemistry,
Zhengzhou University, Zhengzhou 450052, Henan, P. R. China. E-mail:
gangli@zzu.edu.cn
1204

THREE Co(II) SUPRAMOLECULES
1205
SCH. 1. The synthesis of complexes 1–3.
4.01; N, 8.57. Found (%): C, 43.88; H, 3.87; N, 8.76. IR (cm−1
KBr): 3497 w, 2985 w, 1591 m, 1293 m, 1112 m, 873 w, 785 m,
732 s, 542 m.
,
fiber. All data were collected at a temperature of 291(2) K using
the ω-2θ scan technique and corrected for Lorenz-polarization
effects. A correction for secondary extinction was applied.
The structures of compounds 1–3 were solved by direct
methods and expanded using the Fourier technique. The non-
hydrogen atoms were refined with anisotropic thermal parame-
ters. Hydrogen atoms were included but not refined. The final
cycle of full-matrix least-squares refinement was based on 2362
observed reflections and 196 variable parameters for 1, 2797 ob-
served reflections and 225 variable parameters for 2, and 2333
observed reflections and 170 variable parameters for 3. All cal-
culations were performed using the SHELX-97 crystallographic
software package.[21] Selected bond lengths and angles are listed
in Table 2.
Preparation of Crystalline [Co(H2MOPhIDC)2(H2O)2]·
2CH3CN (2)
A mixture of H3MOPhIDC (52.4 mg, 0.2 mmol),
CoCl2·6H2O (23.8 mg, 0.1 mmol), Et3N (0.056 mL, 0.4 mmol),
and CH3CN/H2O (4:4, 8 mL) was sealed in 25 mL Teflon-lined
bomb, which was heated to 160◦C for 4 days, and then cooled
to room temperature at a rate of 10◦C/h. Pink crystals of 2
were obtained and dried in air. Yield: 64%. Anal. Calcd. (%)
for C28H26N6O12Co: C, 48.22; H, 3.76; N, 12.05. Found (%):
C, 47.92; H, 3.53; N, 11.87. IR (cm−1, KBr): 3205 s, 2963 m,
2256 w, 1607 s, 1570 s, 1525 m, 1465 m, 1391 m, 1261 s, 1070 s,
800 s, 634 m.
RESULTS AND DISCUSSION
Preparation of Crystalline [Co(H2PhIDC)4(H2O)] (3)
Synthesis
A
mixture of H3PhIDC (36.8 mg, 0.2 mmol),
In general, under hydrothermal synthesis conditions the
phenyl-substituted imidazole dicarboxylate ligand at 2-position
usually shows various coordination modes and can reacts with
metal ions to obtain relatively complicated coordination poly-
mers or polynuclear complexes, but in this study, only three
mononuclear complexes were obtained. This indicates that un-
der the hydrothermal conditions, the factors governing the reac-
tion and formation of the hydrothermal product are complicated.
It is well known that the coordination environments of metal
centers, position and type of functional groups on the ligands,
Co(NO3)2·6H2O (34.6 mg, 0.2 mmol), Et3N (0.056 mL,
0.4 mmol), and CH3CN/H2O (5:2, 7 mL) was sealed in 25 mL
Teflon-lined bomb and heated at 160◦C for 4 days, and then
cooled to room temperature at a rate of 10◦C/h. Pink crystals
of 3 were collected and dried in air. Yield: 53%. Anal. Calcd.
for C22H16N4O9Co (%): C, 49.00; H, 2.99; N, 10.39. Found:
C, 49.28; H, 2.72; N, 10.02. IR (cm−1, KBr): 3440 s, 2847 w,
1570 s, 1446 w, 1374 w, 1245 w, 1221 w, 837 s, 699 s.
X-Ray Crystallography
Crystal data and experimental details for compounds 1–3 and the ratio between metal salts and ligands, templates, solvent
are contained in Table 1. All measurements were made on a system, counterions, temperature, reaction time, and pH value
Bruker smart APEXII CCD diffractometer (Germany) with a can direct the generation of supramolecular frameworks.
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å).
In addition, in complexes 1 and 2, the central metal Co(II)
Single crystals of 1–3 were selected and mounted on a glass ions are six-coordinated, but in 3, the central Co(II) ion is

1206
Z. XIONG ET AL.
TABLE 1
Crystallographic data for complexes 1–3
1
2
3
Formula
Fw
C24H26O14N4Co
653.42
C28H26O12N6Co
C22H16O9N4Co
697.48
539.32
Crystal system
Space group
Crystal size (mm)
a (Å)
Triclinic
P-1
Triclinic
P-1
Orthorhombic
C222(1)
0.21 × 0.18 × 0.15
6.4019(10)
9.5963(14)
11.2096(17)
75.763(2)
83.277(2)
73.582(2)
639.45(17)
1
0.24 × 0.21 × 0.18
0.21 × 0.18 × 0.17
7.309(14)
11.5089(10)
b (Å)
8.960(18)
12.62(2)
106.22(2)
93.24(2)
111.70(2)
725(2)
6.9132(8)
25.646(3)
c (Å)
α (◦)
90
90
90
β (◦)
γ (◦)
V (Å3)
Z
2040.5(4)
1
4
Dc (mg m−3
F(000)
)
1.697
337
0.756
1.597
359
0.669
1.756
1100
0.910
µ (mm−1
)
Reflections collected unique 5070/2362 R(int) = 0.0245
5468/2797 [R(int) = 0.0225]
7298/2333 [R(int) = 0.0345]
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
2362/0/204
1.018
2797/0/266
2333/0/170
1.117
1.006
R1 = 0.0387; wR2 = 0.1042
R1 = 0.0347; wR2 = 0.0916
R1 = 0.0331; wR2 = 0.0718
R1 = 0.0471; wR2 = 0.1175
R1 = 0.0417; wR2 = 0.0953
R1 = 0.0417; wR2 = 0.0753
penta-coordinated. This may be due to the different anions of two imidazole rings is 0.0◦, which shows that the two imidazole
metal salts [CoCl2, Co(NO3)2]. However, the role of anion ions rings are parallel to each other. The bond lengths and angles
in the formation of different coordination number of central within the H2MOPhIDC− ligand are similar to these reported
metal ions is ambiguous. The three mononuclear complexes compounds.[17]
are stable in the air.
As shown in Figure 2, the intramolecular and intermolecular
H-bonds, and weak stacking between the phenyl rings supply the
additional stability effect for the solid-state structure of complex
1. To the best of our knowledge, the ligand H3MOPhIDC was
first used to prepare Co complexes by us.
Crystal Structure of [Co(H2MOPhIDC)2(H2O)2]·2H2O (1)
The structure determination of 1 reveals this molecule crys-
tallizes in the space group P–1. An ORTEP drawing of the
molecular structure with atom labeling scheme is shown in
Figure 1.
Crystal Structure of [Co(H2MOPhIDC)2(H2O)2]·2CH3CN
The Co(II) ion is six-coordinated, adopting a slightly dis-
torted octahedral geometry. The equatorial plane is defined by
two nitrogen atoms (N1, N1A) and two oxygen atoms (O1, O1A)
(2)
The Co(II) atoms of complex 2 is also six-coordinated like
from two individual H2MOPhIDC− ligands. The axial positions complex 1. As is shown in Figure 3, the coordination envi-
are occupied by two water molecules. The Co—O bond lengths ronment around the Co(II) ion can be described as a slightly
vary from 2.0438(18) to 2.0954(19) Å and the Co1—N1 bond distorted octahedron. The equatorial plane is occupied com-
length is 2.286(2) Å, which is comparable to the previously re- pleted by two imidazolate nitrogen (N1A, N1) atom and two
ported values. The bond angles around the central Co(II) ion carboxylate oxygen atoms (O1A, O1) from two chelating
vary from 78.18(7)◦ to 180.00(16)◦.
H2MOPhIDC−, and two oxygen atom from two water molecule
It should be pointed out that the carboxylate shows bidentate occupying the axial positions. The Co—O bond lengths vary
coordination mode. Within the organic ligand, the dihedral angle from 2.046(4) to 2.086(4), which is narrower than coordination
between the imidazole ring (the mean deviation from the plane is complex 1, and the Co1—N1A bond lengths are 2.157(3) Å,
0.0120 Å) and the carboxylato plane is 5.9◦ indicating the small which shorter than complex 1. The bond angles around each
twist. The dihedral angle between the imidazole ring and the Co(II) ion vary from 78.03(15) to 180.00(7)◦. Compared with
phenyl plane is 5.2◦. However, the dihedral angle between the complex 1, scope of the bond angle has been increased.

THREE Co(II) SUPRAMOLECULES
1207
TABLE 2
Selected bond distances (Å) and angles (deg) for complexes 1–3
1
Co(1)-O(1) #1
Co(1)-O(6)
2.0438 (18) Co(1)-O(1)
2.0954 (19) Co(1)-N(1) #1
2.0438 (18)
2.286 (2)
88.91 (8)
88.91 (8)
101.82 (7)
101.82 (7)
91.23 (7)
Co(1)-O(6) #1
Co(1)-N(1)
2.0954 (19)
2.286 (2)
91.09 (8)
180.00 (14)
91.23 (7)
78.18 (7)
180.00 (7)
O(1) #1-Co(1)-O(1)
O(1)-Co(1)-O(6) #1
O(1)-Co(1)-N(6)
O(6) #1-Co(1)-N(1)
O(6)-Co(1)-N(1) #1
2
180.000 (16) O(1)-Co(1)-O(6)
91.09 (8) O(1) #1-Co(1)-O(6)#1
78.18 (7) O(1) #1-Co(1)-N(1)
88.77 (7) O(1)-Co(1)-N(1) #1
88.77 (7) O(6) #1-Co(1)-N(1) #1
O(1) #1-Co(1)-O(6)
O(6)-Co(1)-O(6) #1
O(6)-Co(1)-N(1)
O(1) #1-Co(1)-N(1) #1
N(1)-Co(1)-N(1) #1
Co(1)-O(11) #1
Co(1)-O(1)#1
2.046 (4) Co(1)-O(11)
2.086 (4) Co(1)-N(1)
2.046 (4)
2.157 (3)
Co(1)-O(1)
Co(1)-N(1)#1
2.086 (4)
2.157 (3)
O(11)-Co(1)-O(11)#1
O(11)-Co(1)-O(1)
O(11) #1-Co(1)-N(1) #1
O(1)#1-Co(1)-N(1) #1
O(1)-Co(1)-N(1)
3
180.000 (1) O(11)-Co(1)-O(1)
89.56 (10) O(11)#1-Co(1)-O(1)#1
89.13 (12) O(11)-Co(1)-N(1) #1
78.03 (15) O(11) #1-Co(1)-N(1)
78.03 (15) O(1)#1-Co(1)-N(1)
89.56 (10)
89.56 (10)
90.87 (15)
90.87 (12)
101.97 (15)
O(11)#1-Co(1)-O(1)
O(1)-Co(1)-O(1)#1
O(1)-Co(1)-N(1) #1
O(11)-Co(1)-N(1)
N(1)-Co(1)-N(1)#1
90.44 (10)
180.00 (7)
101.97 (15)
89.13 (12)
180.000 (1)
Co(1)-O(5)
Co(1)-N(1)#1
1.979 (2) Co(1)-O(1)
2.1497 (18) Co(1)-N(1)
122.77 (5) O(5)-Co(1)-O(1)#1
93.60 (5) O(1)-Co(1)-N(1)#1
93.60 (5) O(1)-Co(1)-N(1)
172.80 (10) C(1)-O(1)-Co(1)
107.04 (16)
2.0013 (18)
2.1497 (18)
122.77 (5)
94.93 (8)
81.14 (7)
116.47 (15)
Co(1)-O(1) #1
2.0013 (17)
O(5)-Co(1)-O(1)
O(5)-Co(1)-N(1)#1
O(5)-Co(1)-N(1)
N(1)#1-Co(1)-N(1)
C(2)-N(1)-Co(1)
O(1)-Co(1)-O(1)#1
O(1)#1-Co(1)-N(1)#1
O(1)#1-Co(1)-N(1)
C(5)-N(1)-Co(1)
114.45 (11)
81.14 (7)
94.93 (8)
146.56 (17)
Symmetry transformations used to generate equivalent atoms for 1: #1: –x + 1, –y, –z. For 2: #1: –x + 1, –y + 2, –z. For 3: #1: x, –y, –z + 2.
It is noteworthy that the dissolubility of the starting mate- angles within the phenyl group are unexceptional and similar to
rials is important for the formations of complexes. We found those of complex 1.
out that the carboxylate of H2MOPhIDC− is bidentate coor-
As shown in Figure 4, the soild-state packing of the com-
dination mode. Within one H2MOPhIDC−, the dihedral angle pound 2 is supported by intermolecular interactions. We can see
between the imidazole ring (the mean deviation from the plane clearly that the IR spectrum of complex 2 is mostly consistent
is 0.0120 Å) and the carboxylato plane is 5.1◦, indicating the with 1 in the main characteristic absorptions. The difference is
large twist. The dihedral angle between the imidazole ring and
the phenyl plane is 34.7◦. However, the dihedral angle between
the two imidazole rings is 0.0◦. In addition, the bond lengths and
FIG. 1. Perspective view of compound 1 (color figure available online).
FIG. 2. The crystal packing of compound 1 (color figure available online).

1208
Z. XIONG ET AL.
FIG. 5. Perspective view of compound 3 (color figure available online).
bond: the intramolecular H-bonds consist of O(3)–H(3). . .O(2)
and N(2)-H(2A). . .O(4)#2 between the two ligands and the in-
termolecular H-bond includes O(5)–H(1W). . .O(2)#3 and weak
stacking between the imidazole rings or phenyl rings supply the
additional stability effect for the solid-state structure of com-
pound 3.[22]
FIG. 3. Perspective view of compound 2 (color figure available online).
IR Spectroscopy
that in 2 there are acetonitrile solvent molecules is instead of
water solvent molecules in 1. This means that the two complexes
have similar coordination modes. The strong absorption bands
around 1670 cm−1 are assigned to mas(COO−) vibrations for
the carboxyl groups.
The IR spectra of compounds 1–3 display characteristic ab-
sorption bands for phenyl rings and carboxylate units. The coor-
dination of the carboxylate units can be seen from the absorption
bands in the frequency range 1295–1623 cm−1 in complexes due
to νas(COO−) and νs(COO−) vibrations, respectively. The car-
bonyl stretching vibration peak of complexes is at 1670 cm−1
.
Crystal Structure of [Co(H2PhIDC)2(H2O)] (3)
The characteristic vibration of phenyl ring in complexes is found
around 1530 cm−1. Compounds 1–3 show strong and broad ab-
sorption bands in the range of 3400–3500 cm−1, which indi-
cate the presence of the νN–H and the νO–H stretching frequen-
cies of the imidazole ring and coordinated water molecules,
A perspective view of the molecular structure of 3 is pre-
sented in Figure 5. The Co(II) ion is five-coordinated by two
imidazolate nitrogen atoms and two oxygen atoms from two in-
dividual H2PhIDC−, and one water molecule. The Co—O bond
lengths vary from 1.979(2) to 2.0013(18) Å and the Co-N bond
lengths are 2.1497(18) Å. The bond angles around each Co(II)
ion vary from 81.14(7) to 122.77(7)◦.
Usually, the Co(II) coordination complexes are mainly built
by carboxylate-based and N-containing ligands. For example,
Han et al. described the synthesis and structure of a 3D chi-
ral Co(II) coordination polymer [Co(hip)(DPPZ)]n (H2hip =
5-hydroxyisophthalic acid, DPPZ = dipyridophenazine).[23]
Complex 3 is the first example of a Co(II) mononuclear complex
with H3PhIDC.
As shown in Figure 6, there are two kinds of hydrogen bonds
in complex 3: intramolecular H-bond and intermolecular H-
FIG. 4. The packing of compound 2 (color figure available online).
FIG. 6. The packing of compound 3 (color figure available online).

THREE Co(II) SUPRAMOLECULES
1209
FIG. 8. The fluorescent spectra of the organic ligand H3MOPhIDC and com-
plexes 1 and 2 (color figure available online).
FIG. 7. TG-DSC curves of compounds 1–3 (color figure available online).
respectively. In conclusion, the infrared spectral data
(400–4000 cm−1) of the three complexes are consistent with
crystal structure analyses.
corresponding to the decomposition of the H2PhIDC− units.
Finally, a plateau region is observed from 533.5 to 640.0◦C. A
brown amorphous residue is Co2O3 (observed 15.23%, calcu-
lated 15.38%).[23]
Thermogravimetric Analysis
TG curve of complex 1 shows four-step weight loss process
(Figure 7). Complex 1 is stable until 163.7◦C, then first and the
second lose weight from 163.7 to 258.9◦C, the total weight loss
of the both steps is 11.23% and calculated 11.03%, they are cor-
responding to losses of two crystallization methanol molecule
and two coordination water molecules. The third and the four
weight loss step are from 258.9 to 387.0◦C, the total weight
loss of the both steps is 75.18%, which corresponds to the de-
composition of the organic ligands. Finally, a plateau region is
observed from 480.0 to 640.0◦C. A brown amorphous residue
is 0.5Co2O3 (observed 13.59%, calculated 12.69%).
The TG curve of complex 2 shows three-step weight loss pro-
cess (Figure 7). The complex is stable until 155.5◦C, and then
loses weight from 155.5 to 287.3◦C (observed 16.08%, calcu-
lated 16.93%) corresponding to losses of two crystallization
acetonitrile and two coordination water molecules. The second
and the third weight loss steps are from 287.3 to 382.7◦C and
from 382.7 to 459.8◦C, respectively. The total weight loss of
the both steps is 71.34%, which corresponds to the decomposi-
tion of the H2MOPhIDC− ligands. Finally, a plateau region is
observed from 459.8 to 620◦C. A brown amorphous residue is
0.5Co2O3 (observed 12.58%, calculated 11.89%).
Photoluminescent Properties
The fluorescence properties of complexes 1–3 and the corre-
sponding ligand H3MOPhIDC were examined in the solid state
at room temperature.
As shown in Figure 8, the free H3MOPhIDC ligand shows
luminescence with the emission maximum at 375 nm by se-
lective excitation at 280 nm, which is attributed to the π∗→n
transition. The compound 1 has a broad emission band in the
range of 375–415 nm with a maximum at 405 nm upon exci-
tation at 280 nm. In the case of compound 2, a weak emission
band with a maximum at 415 nm upon excitation at 290 nm was
observed. Compared with the emission spectrum of H3MOIDC,
red shifts of 30 nm and 40 nm in 1 and 2, respectively, have been
observed. The emission can be assigned to the ligand-to-metal
charge transfer (LMCT), rather than the π∗→n transition of the
ligand. Unfortunately, for compound 3, very weak fluorescence
intensity was observed.[24]
CONCLUSION
By reaction of imidazole-based cayboxylate with cobalt(II)
metal ion under hydrothermal conditions, three pink crystalline
products have been successfully prepared and characterized.
The elemental analysis, IR, and thermal data are consistent with
the X-ray analysis results. The results indicate the 2-position
phenyl imidazole dicarboxylates are very effective ligands for
preparing novel complexes.
The TG curve of complex 3 shows four-step weight loss pro-
cess (Figure 7). The complex is stable until 101.2◦C, and then
loses weight from 87.8 to 141.7◦C; the total weight loss is 3.75%
and calculated 3.34% corresponding to the loss of one coordina-
tion water molecule. The next three weight loss steps are from
141.7 to 299.5◦C, from 299.5 to 369.9◦C, and from 369.9 to
463.5◦C (the total weight loss of the three steps being 81.02%)

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13. Lu, W.G.; Jiang, L.; Feng, X.L.; Lu, T.B. Four 3D Porous metal-organic
frameworks with various layered and pillared motifs. Cryst. Growth Des.
2008, 8, 986–994.
Crystallographic data for the structure reported in this arti-
cle in the form of CIF file has been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publi-
cation Nos. 867408–867410 for complexes 1–3, respectively.
Copy of the data can be obtained free of charge on application
to CCDC, 12 Union Road, Cambridge CB2 IEZ, UK (Fax: +44
1223 336 033; E-mail: deposit@ccdc.cam.ac.uk).
14. Yue, S.T.; Wei, Z.Q.; W, N.; Liu, W.J.; Chang, L.M.; Liu, Y.L.; Mo, H.H.;
Cai, Y.P. Three novel microporous 3D heterometallic 3d-4f coordination
polymers: synthesis, crystal structures and photoluminescence properties.
Inorg. Chem. Commun. 2011, 14, 1396–1399.
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