Three coordination polymers of transition metals built using HPPC ligand: Crystal structures and novel topology

Article abstract of DOI:10.1016/j.poly.2014.05.040

A new pyrazole-carboxylate type ligand, 3-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (HPPC) was prepared from 3-acetylpyridine, diethyl oxalate and hydrazine hydrate. By employing this ligand, three new coordination complexes were prepared under solvothermal conditions: {[Ni(PPC)₂]·3H₂O}_n (1), [Ag(PPC)]_n (2) and [Cd(PPC)Cl]_n (3). Single-crystal X-ray diffraction analyses reveal that 1-3 exhibit three different structural types. Complex 1 displays a 4-connected net with the Schl?fli symbol (4⁴·6²) topology, several types of hydrogen bonds connect the 2-D layer to a 3-D structure. Complex 2 is built from [Ag(N₂O)] clusters and PPC ligand as 3-connected linker with Schl?fli symbol {3⁶·4⁶·5³} without consideration of Ag?Ag interaction. The 2-D networks are also linked to form 3 D framework via Ag?Ag interaction. Complex 3 can be regarded as a (3, 3)-connected net with the Schl?fli symbol {3³³·4³³}, which consists of [Cd(N₂O₂)] clusters and PPC ligand as 3-connected bridge. The layers are further linked by the cholride atoms to generate a 3-D network.

Full text of DOI:10.1016/j.poly.2014.05.040

Accepted Manuscript
Three coordination polymers of transition metals built using HPPC ligand:
Crystal structures and novel topology
Hong Zhao, Zhao-Jing Chu, Gui-Yuan Gao, Huan-Huan Huang, Zhi-Rong Qu
PII:
S0277-5387(14)00357-X
http://dx.doi.org/10.1016/j.poly.2014.05.040
POLY 10755
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
26 March 2014
20 May 2014
Please cite this article as: H. Zhao, Z-J. Chu, G-Y. Gao, H-H. Huang, Z-R. Qu, Three coordination polymers of
transition metals built using HPPC ligand: Crystal structures and novel topology, Polyhedron (2014), doi: http://
dx.doi.org/10.1016/j.poly.2014.05.040
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Three coordination polymers of transition metals built using
HPPC ligand: Crystal structures and novel topology
Hong Zhaoa*, Zhao-Jing Chu,a Gui-Yuan Gao,a Huan-Huan Huang,a Zhi-Rong Qub
aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, P.R.
China, and bKey Laboratory of Organosilicon Chemistry and Material Technology of
Ministry of, Education Hangzhou Normal University, Hangzhou, 311121, P.R. China
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Abstract
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A new pyrazole-carboxylate type ligand, 3-(pyridin-3-yl)-1H-pyrazole-5-carboxylic
acid (HPPC) was prepared from 3-acetylpyridine, diethyl oxalate and hydrazine
hydrate. By employing this ligand, three new coordination complexes were prepared
under solvothermal conditions: {[Ni(PPC)2]·3H2O}n (1), [Ag(PPC)]n (2) and
[Cd(PPC)Cl]n (3). Single-crystal X-ray diffraction analyses reveal that 1–3 exhibit
three different structural types. Complex 1 displays a 4-connected net with the
Schläfli symbol (44·62) topology, several types of hydrogen bonds connect the 2-D
layer to a 3-D structure. Complex 2 is built from [Ag(N2O)] clusters and PPC ligand
as 3-connected linker with Schläfli symbol {36·46·53} without consideration of
Ag···Ag interaction. The 2-D networks are also linked to form 3 D framework via
Ag···Ag interaction. Complex 3 can be regarded as a (3, 3)-connected net with the
Schläfli symbol {333·433}, which consists of [Cd(N2O2)] clusters and PPC ligand as
3-connected bridge. The layers are further linked by the cholride atoms to generate a
3-D network
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Corresponding author. Tel.: +86-52090619; fax: +86-52090620.
E-mail address: zhaohong@seu.edu.cn

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23 Keywords: 3-(pyridin-3-yl)-1H-pyrazole-5-carboxylic
acid;
Solvothermal
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conditions; Topological structures; Coordination complexes
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26 1. Introduction
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Metal organic frameworks (MOFs) have been attracting attention because of the
photoluminescence properties [1, 2], magnetism [3, 4], catalysis [5] and gas storage [6,
7] as well as for the variety of their diverse structural topologies [8-10]. Although
rapid progress in MOFs has been made, it is also a great challenge to rationally
prepare and control the structures and configuration of target products in crystal
engineering. The formation of metal organic frameworks greatly depends on the
sophisticated selection and utilization of multifunctional organic ligands. Among the
reported organic ligands, carboxylate complexes and N-donor complexes play
dominant roles in the fabrication of coordination polymers with unique structures
[11-13]. Recently, the pyrazole carboxylic acids [14-17] have been widely used to
build MOFs and topological structures because of several interesting features. They are
good candidates for the assembly of 3d, 4f supramolecular network through hydrogen
bonds. An appropriate angle between O- and Ncoordination sites will provide the
potential for the formation of helix structures [18]. However, there are few reports on
pyridyl group introduced to pyrazole carboxylic acid. One pyridyl group is introduced
to pyrazole carboxylic acid, which enlarges the size of ligand and increases the
possibility of π···π interactions. The pyridyl group may also induce different
conformations of pyrazole carboxylic acid bridging modes due to geometrical
constrains. In addition, pyrazole carboxylate anions may take different effects in the
supramolecular architecture.
Taking all the above into account, we have designed and synthesized the
3-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (HPPC) ligand. Three coordination
polymers {[Ni(PPC)2]·3H2O}n (1), [Ag(PPC)]n (2), [Cd(PPC)Cl]n (3) with different

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topological structures, were prepared by HPPC and three different metal salts
(NiCl2·6H2O, AgNO3, CdCl2·2.5H2O) under solvothermal conditions, respectively.
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53 2. Experimental
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2.1. Materials and characterization
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All chemicals and solvents were commercially available and used without
purification. Elemental analyses for carbon, hydrogen and nitrogen were performed
on a Perkin Elmer 240C elemental analyzer. IR spectra were obtained with KBr
pellets from 4000 to 400 cm-1 using a Shimadzu IR prestige-21 spectrophotometer. All
1H NMR spectra were carried out on a Bruker HW300 MHz spectrometer (AVANCE
AV-300) in CH3COCH3-d6. Thermogravimetric Analysis (TGA) data were recorded
on a SDT-Q600 analyser from TA instruments.
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2.2. Preparation of 3-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (HPPC)
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To a stirred solution of MeONa (3.24 g, 60 mmol) in THF (25 ml), was add
diethyl oxalate (5.84 g, 40 mmol) and the resulting mixture was heated to reflux. At
the reflux temperature, 3-acetylpyridine (3.63 g, 30 mmol) was added, then cooled
and filtered. It was afford 4.6575 g (75%) of 2,4-dioxo-4-pyridin-3-yl-butyric acid
ethyl ester. Hydrazine hydrate (0.8 g, 16 mmol) was added to a solution of
2,4-dioxo-4-pyridin-3-yl-butyric acid ethyl ester (3.726 g, 18 mmol) in acetic acid (20
ml) and stirring at reflux temperature for 3 h, then concentrated under reduced
pressure. The residue obtained was diluted with water, then filtered to afford 1.736 g
(50%) of 3-(pyridin-3-yl)-1H-pyrazole-3-carboxylic acid ethyl ester (PPCAE).
A mixture of NaOH (0.06 g, 15 mmol), PPCAE (1.763 g, 8 mmol), THF (16 ml),
MeOH (15 ml) and H2O (8 ml) was stirred at 65 for 4 h. After removal of the
solvent under reduced pressure. The residue obtained was diluted with water, a cold
aqueous HCl solution (6 mol/L) was used to neutralize the solution to pH=5. The
white precipitate was collected and washed with water to give crude HPPC (1.361 g,

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90%). The crude HPPC was purified on silica gel by column chromatography. PPCAE
(Fig. A.1): 1H-NMR (300MHz, CH3COCH3-d6): δ = 9.12(s, 1H, -C5NH4), 8.57(d, 1H,
-C5NH4), 8.30(s, 1H, -C5NH4), 7.31-7.51(m, 1H, -C5NH4), 7.08(d, 1H, -C3N2H),
4.39-4.49(m, 2H, -CH2), 1.28-1.39(m, 3H, -CH3). HPPC (Fig. A.2): IR (KBr, ν, cm-1):
3423(s), 1724(s), 1573(w), 1438(w), 1389(w), 1337(m), 1292(m), 1243(m), 762(s),
703(s), 636(w). MS(ESI-): m/z (%) = 233.8 [HPPC+HCOOH]-, 223.9 [HPPC+Cl]-,
188.1 [HPPC+H]-.
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2.3. Synthesis of complexes 1-3
2.3.1. For the preparation of the complex 1
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A mixture of HPPC (0.0189 g, 0.1 mmol), NiCl2·6H2O (0.0238 g, 0.1 mmol),
MeOH (10 ml) and H2O (10 ml) was sealed in a 25 ml Teon-lined stainless steel
reactor at 413 K for 72 h. Finally, the reactor was cooled to room temperature. Purple
crystals of the complex were obtained in 45% yield (base on HPPC). Calculated for
C18H16N6NiO7 (487.08): C 44.39, H 3.31, N 17.25%; found: C 44.33, H 3.28, N
17.29%. IR (KBr, ν, cm-1): 3442(m), 1603(s), 1503(m), 1476(m), 1454(w), 1353(m),
1285(w), 1227(m), 1202(m), 1018(s), 969(s), 826(s), 788(s).
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2.3.2. For the preparation of the complex 2
A mixture of HPPC (0.0189 g, 0.1 mmol), AgNO3 (0.034 g, 0.2 mmol), CH3CN
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(10 ml) and H2O (10 ml) was stirred under air atmosphere for half an hour. Then the
solution was transferred to a sealed in a 25 ml Teon-lined stainless steel reactor at
393 K for 48 h. Finally, the reactor was cooled to room temperature. Pale yellow
crystals of the complex were obtained in 40% yield (base on HPPC). Calculated for
C9H5AgN3O2 (295.03): C 36.64, H 1.71, N 14.24%; found: C 36.76, H 1.68, N
14.28%. IR (KBr, ν, cm-1): 3429(w), 3124(m), 1594(s), 1432(w), 1392(s), 1345(s),
1321(w), 1199(m), 1157(m), 1054(m), 976(s), 798(s), 700(m).
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2.3.3. For the preparation of the complex 3
Complex 3 was prepared similarly to complex 2. A mixture of HPPC (0.0189 g,

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0.1 mmol), CdCl2·2.5H2O (0.0228 g, 0.1 mmol), CH3CN (10 ml) and H2O (10 ml)
was employed. Colorless crystals of the complex were obtained in 55% yield (base on
HPPC). Calculated for C9H5CdClN3O2 (335.01): C 32.27, H 1.50, N 12.54%; found:
C 32.02, H 1.55, N 12.49%. IR (KBr, ν, cm-1): 3398(w), 3115(m), 1575(s), 1486(m),
1452(w), 1408(s), 1336(s), 1199(m), 1001(s), 799(s), 679(s).
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2.4. X-ray Data Collection and Structures Refinement
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Single crystal X-ray diffraction analysis of 1-3 were carried out on a Bruker
SMART CCD-4K diffractometer employing a graphite-monochromated Mo-Kα
radiation (λ = 0.71073 Å) at 293(2) K (for 1 and 2) and 296(2) K (for 3). The data
were collected using SMART and reduced by the program SAINT [19]. All the
structures were solved by direct methods and refined by full-matrix least squares
method on F2
using the SHELXTL-PC software package [20, 21]. All
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non-hydrogen atoms were refined anisotropically, whereas all hydrogen atoms were
calculated by geometrical methods and refined as a riding model. The details of
crystal parameters, data collection and refinements for the complexes are summarized
in Table 1; Selected bond distances and angles and hydrogen bonds for the complexes
are given in the Supplementary data (Tables A1 and A2).
121 3. Results and discussion
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3.1. Description of the structures
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3.1.1. Crystal structure description of {[Ni(PPC)2]•3H2O}n (1)
The complex 1 crystallizes in the monoclinic system with the Cc space group,
and displays a novel 2-D topology. Each asymmetric unit consists of a divalent Ni(II)
ion, two deprotonated HPPC ligands (PPC) and three solvent water molecules. As
shown in Fig. 1, Each Ni(II) ion is octahedral coordinated by two nitrogen atoms
(Npyrazole and Npyridin ) leaving two cis-positions for two carboxylate oxygen atoms (O2
and O3) from two PPC ligands, they comprise the equatorial plane. The other two

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nitrogen atoms N3a, N6b (Symmetry codes: (a) x, 2-y, 1/2+z, (b) 1+x, y, z) from two
individual PPC ligands occupy the axial positions. PPC ligands show N,O-chelating
coordination mode, every ligand links two Ni(II) ions. The pyrazole ring together with
its carboxylate group are nearly coplanar, and the dihedral angles between the pyridyl
and pyrazole rings are 74.79(15)° and 45.74(15)°, respectively.
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Each Ni(II) ion is bridged with four adjacent Ni(II) ions via two orientational
PPC ligands formed a 2-D cationic planar structure (Fig. 2). The Ni(II) ions are linked
by the HPPC ligands to a zig-zag chain structure with the Ni···Ni distance of 9.692 Å
along the a-axis, the angles of Ni···Ni···Ni is 112.245°, and to a cavernous structure
along the c-axis. The repeating unit can be described as Ni···PPC···Ni···PPC···Ni.
From the topological view, if Ni(II) ions are viewed as 4-connected nodes and the
PPC ligands considered as linkers, the framework of 1 can be described as a
4-connected net with (44·62) topology (Fig. 3). Water molecules form two
intermolecular hydrogen bonds and four intramolecular hydrogen bonds with
carboxylate oxygen atoms. Each 2-D layer is linked with neighbors via
O—H···O(O5—H5WA···O1a, O5—H5W···O4, O7—H7WA···O4b, O7—H7W···O2)
(Symmetry codes: (a) x, 2-y, 1/2+z, (b) 1+x, y, z) hydrogen-bonding interactions,
constructing a 3-D framework (Fig. A.3).
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3.1.2. Crystal structure description of [Ag(PPC)]n (2)
The reaction of AgNO3 with HPPC ligand yield a 3-D coordination complex.
Complex 2 crystallizes in the monoclinic space group P21/c. As shown in Fig. 4, Ag(I)
is coordinated by one O donor from one PPC ligand [Ag–O = 2.316(2) Å] and two N
donors [Ag–Npyrazole = 2.172(2) Å, Ag–Npyridin = 2.182(2) Å, N–Ag–N = 101.87
(6)-146.54 (8)°] from two different PPC ligands. Ag(I) ion adopts Y-shaped
coordination geometries without consideration of Ag···Ag interaction. A strong
argentophilic interaction exists between Ag1 and Ag1a (Symmetry codes: (a) -x+1,
y-1/2, -z-1/2) with Ag···Ag distance of 3.0512 Å. This Ag···Ag contact distance is
shorter than the sum of the van der Waals radii [22-24] (3.44 Å of two silver atoms).
In complex 2, each PPC ligand bridges three different Ag(I) ions, in turn each Ag(I)

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ion is coordinated to three different PPC ligands. Such kind of connection extends to a
2-D network without consideration of Ag···Ag interaction (Fig. 5).
Both PPC and Ag(I) ion in complex 2 can be regarded as 3-connectors, thus the
network of 2 can be a uninodal 6-connected 2-D network with Point (Schläfli) symbol
of {36·46·53} (Fig. 6) calculated by TOPOS [25-27]. The 2-D networks are also linked
to form 3 D framework via Ag···Ag interaction in the crystal structure (Fig. 7 ).
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3.1.3. Crystal structure description of [Cd(PPC)Cl]n (3)
Single-crystal X-ray diffraction analysis of complex 3 reveals that it contains two
Cd(II) ions, two crystallographically independent PPC ligands and two chloride atoms
in the asymmetric unit. Two Cd(II) ion exhibit similar coordination environments in
the complex 3, Cd1 and Cd2 are six coordinated, forming a slightly distorted
octahedron with a [CdO2N2Cl2] coordination mode. The metal center Cd1
coordinates to six atoms: the two carboxylate groups from the different PPC ligands
provide two donor oxygen atoms (O1 and O4a) (Symmetry codes: (a) -x+1, -y+1,
-z+1), the pyridyl ring and pyrazole ring provide two nitrogen atoms (N1, N6a)
(Symmetry codes: (a) -x+1, -y+1, -z+1) and two chloride atoms. Cd2 is
six-coordinated by two oxygen atoms (O2a and O3) (Symmetry codes: (a) -x+1, -y+1,
-z+1) from different PPC ligands, one nitrogen atom N4 from pyrazole ring, one
nitrogen atom N3a from pyridly ring, and two chloride atoms (Fig. 8). Cd–O bond
lengths range from 2.218(5) Å to 2.400(5) Å, and Cd–N bond lengths range from
2.218(5) Å to 2.380(5) Å, which are within the range of reported coordination
polymers [28-30]. In the complex, PPC ligands adopt N, O-chelating (N1, O1 and N4,
O3) and N, O-bridging (N2, O2 and N6, O4) modes to coordinate to Cd(II) ion. Each
PPC ligand bridges three Cd(II) ion, which leads to 2-D layer structure (Fig. 9).
Topology analysis of 3 using the TOPOS software indicates that it can be
considered as a (3, 3)-connected framework with a {333·433}Schläfli symbol. Each
Cd(II) ion is considered as a 3-connected node while each PPC ligand as 3-connected
linker (Fig. 10). The layers are further linked by the cholride atoms to generate a 3-D
network (Fig. 11).

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3.2. Thermogravimetric analyses
In order to investigate the thermal behavior, complex 1, 2 and 3 were analyzed
by DSC and TGA, with a linear heating rate of 10 K·min–1 in a flowing nitrogen
atmosphere (flow rate 20 mL·min–1). The TGA curves of 1-3 are shown in Fig. 12.
The DSC and TGA curves for complex 1, 2 and 3 are illustrated in supplementary
material (Fig. A.4. for complex 1, Fig. A.5. for complex 2 and Fig. A.6. for complex
3), respectively. For complex 1, a weight loss of 10.9% was observed in the
temperature range of 264-354°C, which corresponds to the loss of three free water
molecules (calcd. 11.1%) and further weight loss was observed at about 360
corresponding to the collapse of the framework. Complex 2 did not show obvious
weight losses before the decomposition of the framework at about 224 indicating no
solvent molecules and being in agreement with the result of the crystal structure. For
complex 3, the TGA curve displays that it was stable up to about 377 and then
began to decomposition of the framework. The second weight loss of 10.3% from 408
to 448 corresponds to the loss of the coordinated chloride atom in 3 (calcd. 10.6%).
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3.3. IR spectra
In the IR spectra of HPPC, absorptions at ca. 3423 cm−1 for the N–H stretching
frequency. The strong bands at 1724 cm−1 in HPPC may be attributed to the
asymmetric stretching (as) mode of the carboxylate group and bands at 1337 cm−1
represent the symmetric stretching (s) mode of this group. The νas(C=N) bands of the
HPPC fall in the range of 1438–1573 cm–1. None of complex 1, 2, 3 shows any strong
bands at ca 1724 cm−1, suggesting that HPPC are deprotonated in the complexes. This
indicates the coordination of the nitrogen atom and oxygen atom to the metal ion,
which shifts νas(C=N) stretch to high lower frequency and νas(C=O) stretch disappear.
IR analysis results are consistent with the crystal structure.
214 4. Conclusions
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In summary, we have synthesized three different coordination complexes of

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Ni(II), Ag(I) and Cd(II) ions, which have different metal-nuclearity using a HPPC
ligand under solvothermal conditions. The ligand exhibits tridentate coordination
mode in the three complexes and leads to the different topologies: a 2-D layer for
complex 1 and a 3D framework for complex 2 and 3. The structures of the resultant
complexes varied from 2D layer to with different topologies. Ni(II) and Cd(II) were
six coordinated, forming a slightly distorted octahedron. Ag(I) has Y-shaped geometry
without consideration of Ag···Ag interaction. Complex 1 displays an undulating layer
structure, which are further stacked by O—H···O hydrogen bonds interactions to
generate a 3D supramolecular architecture.
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65
226
227
Fig. 1. The coordination environment of Ni(II) ion in complex with 40% thermal ellipsoids, the
water molecules and all hydrogen atoms are omitted for clarity (Symmetry codes: (a) x, 2-y, 1/2+z,
(b) 1+x, y, z )
228
229

1
2
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230
231
Fig. 2. View of the 2D undulating layer of complex 1 along the b axis
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234
Fig. 3. The 4-net topology of the complex 1, turquiose particle: Ni; pink line: HPPC ligand

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235
236
Fig. 4. The coordination environment of Ag(I) ion in complex with 40% thermal ellipsoids, all
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hydrogen atoms are omitted for clarity (Symmetry codes: (a) −x+1, y−1/2, −z−1/2; (b) x−1, y, z−1)
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240
Fig. 5. Simplified layer network without Ag---Ag interaction of complex 2
241

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243
Fig. 6. Topological view of 6-connected net in complex 2.
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Fig.7. The 3-D structure contains the Ag---Ag interaction in complex 2. blue: Ag---Ag interaction

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Fig. 8. The coordination environment of Cd(II) ion in complex with 40% thermal ellipsoids, all
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hydrogen atoms are omitted for clarity (Symmetry codes: (a) −x+1, −y+1, −z+1)
251
252
Fig. 9. Simplified layer network without Cd-Cl bridge of complex 3

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Fig. 10. Topological view of (3,3)-connected hcb net in complex 3.
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257
Fig. 11. The framework structure contains the Cd-Cl bridge in complex 3

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Fig. 12. TG curves of complexes 1-3
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262
Acknowledgements
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265
We gratefully acknowledge the financial support of the National Natural Science
Foundation of China (20801012) and the financial support from Jiangsu Ainaji
Neoenergy Science & Technology Co., Ltd (8507040091).
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271
Appendix A. Supplementary
Crystallographic data (excluding structure factors) for the structures in this paper
have been deposited with the Cambridge Crystallographic Data Centre, CCDC, 12
Union Road, Cambridge CB21EZ, UK. CCDC 969973, 981365, and 981366 contains
the supplementary crystallographic data for complexes 1, 2, and 3. (Fax:
+44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
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273
Table 1
Crystallographic data and structure refinement parameters for the complexes

1
2
3
4
5
6
7
8
9
Complex
1
2
3
Empirical formular
Formula weight
Crystal size/mm3
Temperature/K
Crystal system
Space group
[Ni(C18H10N6O4)]·3H2O C9H5AgN3O2
C9H5CdClN3O2
335.01
487.06
295.03
0.30×0.28×0.18
293(2)
0.22×0.35×0.42
293(2)
0.26×0.23×0.22
296
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
Monoclinic
Cc
Monoclinic
P21/n
triclinic
P-1
a / Å
b / Å
c / Å
α/°
8.795(3)
14.240(4)
15.999(5)
90
6.9563 (12)
10.8528 (19)
12.9007 (17)
90
9.774 (2)
10.594 (2)
10.908 (2)
82.495 (2)
64.825 (2)
78.043 (2)
998.9 (4)
β /°
96.677(3)
90
119.305 (7)
90
γ/°
V / Å3
1990.1(11)
849.3 (2)
Z
4
4
4
Dcalc /g·cm–3
ꢀ/ mm-1
1.626
1.032
2.6 to 25.5
7063
3215
3090
1000
2.307
2.35
2.228
2.44
θ range/°
2.6 to 26
6142
2.0 to 25.0
Reflections collected
Independent reflections
Observed reflections
F(000)
6959
1644
3443
1506
2866
572
644
Data/restraints/parameters 3215/2/295
Goodness-of-fit on F2
1644/0/136
1.067
3443/0/289
1.023
1.12
R(all data)
R1=0.0273,wR2=0.0599 R1=0.024,wR2=0.0559
R1=0.0506,wR2=0.1395
R indexes [I>2σ(I)]
R1=0.0260,wR2=0.0594 R1=0.0217,wR2=0.0549 R1=0.0432,wR2=0.1357
274
275 References
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287
[1] M. D. Allendorf, C. A. Bauer, R. K. Bhakta, R. J. Houk, Chem. Soc. Rev. 38 (2009) 1330-1352.
[2] Y. Cui, Y. Yue, G. Qian, B. Chen, Chem. Rev. 112 (2012) 1126-1162.
[3] M. Kurmoo, Chem. Soc. Rev. 38 (2009) 1353-1379.
[4] Y. F. Zeng, X. Hu, F. C. Liu, X. H. Bu, Chem. Soc. Rev. 38 (2009) 469-480.
[5] H. Y. Kim, S. Kim, K. Oh, Angew Chem Int Ed Engl. 49 (2010) 4476-4478.
[6] S. Ma, H. C. Zhou, Chem. Commun (Camb). 46 (2010) 44-53.
[7] J.L. Rowsell, O. M. Yaghi, Angew Chem Int Ed Engl, 44 (2005) 4670-4679.
[8] F. Guo, F. Wang, H. Yang, X. Zhang, J. Zhang, Inorg. Chem. 51 (2012) 9677-9682.
[9] H. J. Zhao, J. P. Ma, Q. K. Liu, Y. B. Dong, Acta Crystallogr., Sect. C. 69 (2013) 716-720.
[10] Z. N. Zheng, S. W. Lee, Polyhedron, 69 (2014) 197-204.
[11] Y.-J. Mu, X.-L. Ma, B. Han, G.-F. Qin, Y.-Y. Niu, H.-X. Lü, Polyhedron, 67 (2014) 44-50.
[12] R. Mishra, M. Ahmad, M. R. Tripathi, R.J. Butcher, Polyhedron, 50 (2013) 169-178.

1
2
3
4
5
6
7
8
9
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
[13] T. Kojima, T. Yamada, Y. Yakiyama, E. Ishikawa, Y. Morita, M. Ebihara, M. Kawano,
CrystEngComm (2014).
[14] X.-H. Li, Acta Crystallogr., Sect. E. 61 (2005) m2329-m2331.
[15] Z.P. Li, Y.H. Xing, Y.H. Zhang, G.H. Zhou, C.G. Wang, J. Li, X.Q. Zeng, M.F. Ge, S.Y. Niu, J.
Coord. Chem. 62 (2009) 564-576.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
[16] C.-B. Liu, Y.-N. Gong, Y. Chen, H.-L. Wen, Inorg. Chim. Acta. 383 (2012) 277-286.
[17] L.-F. Liu, B. Cai, C.-S. He, J.-Z. Wu, Q.-M. Wang, Y. Yu, Inorg. Chim. Acta. 30 (2013) 105-110.
[18] L. Pan, T. Frydel, M. B. Sander, X. Huang, J. Li, Inorg. Chem. 40 (2001) 1271-1283.
[19]SAINT, version 6.02, Bruker AXS, Madison, WI, 1999.
[20] XPREP, version 5.1, Siemens Industrial Automation Inc., Madison, WI, 1995.
[21] G. M. Sheldrick, SHELXL-97: Program for Crystal Structure Refinement, University of
Gottingen, Germany, 1997.
[22] Y. Zorlu, H. Can, F. Aksakal, J. Mol. Struct. 1049 (2013) 368-376.
[23] A. Bondi, J. Phys. Chem. 68 (1964) 441-451.
[24] P. Gutta, R. Hoffmann, J. Phys. Chem. A. 107 (2003) 8184-8190.
[25] V. Blatov, J. Appl. Crystallogr, 33 (2000) 1193.
[26] V.A. Blatov, IUCr CompComm Newsletter, 7 (2006).
[27] V.A. Blatov, TOPOS, A Multipurpose Crystallochemical Analysis with the Program Package,
Samara State University, Russia, 2009.
[28] H.-L. Jia, M.-J. Jia, G.-H. Li, Y.-N. Wang, J.-H. Yu, J.-Q. Xu, Dalton Trans., 42 (2013) 6429-6439.
[29] C.-Q. Wan, A.-M. Li, S.A. Al-Thabaiti, T.C. Mak, Cryst. Growth Des. 13 (2013) 1926-1936.
[30] Y.-Y. Liu, B. Liu, J. Yang, J.-F. Ma, Polyhedron, 56 (2013) 96-101.

In this paper, we report three polymers which were obtained by
3-(pyridin-3-yl)-1H-pyrazole-5-carboxylic acid (HPPC) and M (NiII, AgI, CdII) under
solvothermal conditions. The different coordination modes of HPPC result in one 2-D
polymer and two 3-D polymers.