Two new coordination polymers based on pyridylcarboxylate and imidazole-containing ligand

Article abstract of DOI:10.1080/15533174.2013.771670

Two new metal coordination polymers [Cd(2,3-PDB)(bib)]_n (1) and [Ni(2,5-PDB)(bib)_0.5(H₂O)₂]_n(2) [2,3-PDB = pyridine-2,3-dicarboxylate, 2,5-PDB = pyridine-2,5-dicarboxylate, and bib = 1,4-bis (imidazol-1-yl)benzene] have been successfully synthesized and structure characterized by IR, elemental analysis and X-ray diffraction. Complex 1 shows a two-dimensional wave-like layer and complex 2 exhibits a one-dimensional chain. In 2, the intermolecular hydrogen bonding interactions assemble the one-dimensional chains to three-dimensional supramolecule structure. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2013.771670

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Two New Coordination Polymers Based on
Pyridylcarboxylate and Imidazole-Containing Ligand
Miaomiao Zhang a & Feng Guo a
a Key Laboratory of Coordination Chemistry and Functional Materials in Universities of
Shandong , Dezhou University , Shandong , P. R. China
Accepted author version posted online: 16 May 2013.Published online: 06 Nov 2013.
To cite this article: Miaomiao Zhang & Feng Guo (2014) Two New Coordination Polymers Based on Pyridylcarboxylate and
Imidazole-Containing Ligand, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:3, 397-401,
DOI: 10.1080/15533174.2013.771670
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:397–401, 2014
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.771670
Two New Coordination Polymers Based on
Pyridylcarboxylate and Imidazole-Containing Ligand
Miaomiao Zhang and Feng Guo
Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong,
Dezhou University, Shandong, P. R. China
fashions (cis- and trans-configuration) via bond rotation of the
terminal imidazolyl rings.[10–12] The carboxylate ligands have
also received much attention in the designed synthesis of metal-
organic frameworks due to their many coordination modes, such
as monodentate, chelating, and/or bridging, which allows a wide
variety of structures.[13–15] In this study, we use carboxylate and
1,4-bis (imidazol-1-yl)benzene ligands to construct two new
coordination polymers, [Cd(2,3-PDB)(bib)]n (1) and [Ni(2,5-
PDB)(bib)0.5 (H2O)2]n (2).
Two new metal coordination polymers [Cd(2,3-PDB)(bib)]n
(1) and [Ni(2,5-PDB)(bib)0.5(H2O)2]n(2) [2,3-PDB = pyridine-2,3-
dicarboxylate, 2,5-PDB = pyridine-2,5-dicarboxylate, and bib =
1,4-bis (imidazol-1-yl)benzene] have been successfully synthesized
and structure characterized by IR, elemental analysis and X-ray
diffraction. Complex 1 shows a two-dimensional wave-like layer
and complex 2 exhibits a one-dimensional chain. In 2, the in-
termolecular hydrogen bonding interactions assemble the one-
dimensional chains to three-dimensional supramolecule structure.
Keywords cadmium (II), crystal structure, imidazole-containing lig-
and, nickel (II)
EXPERIMENTAL
Materials and Physical Measurements
All reagents and solvents employed were commercially avail-
able and used without further purification. Elemental analysis
was carried out on a Carlo-Erba 1106 full-automatic trace or-
ganic elemental analyzer. FT-IR spectra were recorded with a
Bruker Equinox 55 FT-IR spectrometer as a dry KBr pellet in
the 400∼4000 cm−1 range.
INTRODUCTION
In past decades, the design and synthesis of metal-organic
frameworks have received considerable attention due to their
potential applications in magnetism, gas separation and lu-
minescence.[1–6] The exploitation of various kinds of organic
ligands is of vital importance to increase the structural di-
versity of coordination polymers, which meanwhile provides
new insights into the relationships between the structure and
the corresponding function. Among organic ligands, imidazole-
containing ligands have proven to be good candidates for the
construction of new metal-organic frameworks due to their di-
verse coordination modes. A large number of CPs based on
the imidazole-containing ligands have constructed.[7–9] The CPs
constructed by rigid bidentate 1,4-bis (imidazol-1-yl)benzene
(bib) are less reported. The reported results shows that rigid
neutral bis(imidazole) ligand exhibits the special ability to co-
ordination to various metal centers in two typical coordination
Syntheses
Synthesis of [Cd(2,3-PDB)(bib)]n (1)
The mixtures of Cd(NO3)2·4H2O (0.5 mmol, 0.145 g), 2.3-
PDB (0.5 mmol, 0.0836 g), bib (0.5 mmol, 0.105 g), NaOH
(1 mmol, 0.04 g), and 12 mL of water were heated to 160◦C
for four days, and then cooled to room temperature. The yel-
low crystals were obtained in pure phase, washed with wa-
ter and ethanol, and dried at room temperature. Anal. Calcd.
for C19H13CdN5O4: C, 46.79; N, 14.36; H, 2.69. Found: C,
46.82; N, 14.37; H, 2.70. IR/cm−1 (KBr): 1627 s,1551 s, 1403 s,
1342 m, 1173 m, 1097 m, 942 m, 820 m, 714 m, 655 m,
Synthesis of [Ni(2,5-PDB)(bib)0.5(H2O)2]n (2)
The mixtures of Ni(NO3)2.6H2O (0.5 mmol, 0.145 g), 2.5-
Received 21 January 2013; accepted 27 January 2013.
The authors thank the support of this work by the Natural Science PDB (0.5 mmol, 0.0836 g), bib (0.5 mmol, 0.105 g), NaOH
(1 mmol, 0.04 g), and 12 mL of water were heated to 160◦C
Foundation of Shandong Province (ZR2011BL024) and the finance
support from Dezhou University (318019).
Address correspondence to Feng Guo, Key Laboratory of Coordi-
nation Chemistry and Functional Materials in Universities of Shan-
dong, Dezhou University, Shandong 253023, P. R. China. E-mail:
guofeng1510@yeah.net
for four days, and then cooled to room temperature. The green
crystals were obtained in pure phase, washed with water and
ethanol, and dried at room temperature. Anal. Calcd. for C13
H12NiN3O6: C, 42.79; H, 3.31; N, 11.51. Found: C, 42.81; H,
397

398
M. ZHANG AND F. GUO
3.30; N,11.50. IR/cm−1 (KBr): 3054 br, 1610 s, 1574 s, 1322 s,
1275 s, 1157 m, 991 m, 807m, 773m, 676 m.
TABLE 1
Crystallographic data and structure refinement summary for
complexes 1 and 2
Empirical formula
C19H13CdN5O4
C13H12NiN3O6
X-Ray Crystallography
Single-crystal X-ray diffraction analyses of complex 1 was Formula weight
carried out on a Bruker SMART APEXII CCD diffractome- Crystal system
ter equipped with a graphite-monochromated Mo-Kα radiation Space group
487.74
Orthorhombic,
Pnma
364.97
Triclinic, P–1
(λ = 0.71073 Å) by using a ω-scan mode. Empirical absorption
correction was applied using the SADABS programs.[11] All the
structures were solved by direct methods and refined by full-
matrix least-squares methods on F2 using the program SHEXL
97.[12] All non-hydrogen atoms were refined anisotropically. The
hydrogen atoms were located by geometrically calculations, and
their positions and thermal parameters were fixed during the
structure refinement. The crystallographic data and experimen-
tal details of structural analyses for coordination polymers are
summarized in Table 1. Selected bond and angle parameters are
listed in Table 2.
Unit cell
dimensions
a = 15.855 (1) Å a = 6.9444 (5))Å
b = 14.161 (2) Å b = 7.2209 (5)Å
c = 7.694 (2) Å
β = 90◦
c = 15.6283 (10)Å
α = 81.4330 (8)◦
β = 79.1437 (8)◦
γ = 62.7916 (7)◦
682.72 (8)
Volume (Å3)
Z
1727.5 (14)
4
2
Calculated density
1.875
1.775
(mg/m3)
Independent
reflections (I >
2σ(I))
1938
2819
RESULTS AND DISCUSSION
F(000)
968
374
θ range for data
collection
Limiting indices
2.57–27.53
1.33–27.61
Description of the Crystal Structure
[Cd(2,3-PDB)(bib)]n (1)
−20 ≤ h ≤ 19
−14 ≤ k ≤ 18
−9 ≤ l ≤ 9
1.069
− 6 ≤ h ≤ 9
−4 ≤ k ≤ 9
−20 ≤ l ≤ 20
1.043
X-ray crystallographic analysis revealed that complex 1 crys-
tallizes in the orthorhombic space group Pnma. The asymmetric
unit contains one 2,3-PDB and one bib ligands. Each Cd(II)
ion is hexacoordinated by three carboxylate oxygen atoms, one
nitrogen of pyridyl ring, and two nitrogen of imidazole rings,
exhibiting a distorted octahedral geometry (Figure 1). The 2,3-
PDB ligands connect the Cd(II) ions to a 1D chain along the
(0,0,1) direction (Figure 2). The bib connect the 1D chains to
2D layer structure along the (0,1,0) direction. Each quadrilateral
Goodness-of-fit on
F2
a
R1 ,wR2 b [I >
R1 = 0.0258
R1 = 0.0265
2σ(I)]
wR2 = 0.0660
wR2 = 0.0714
R1 = 0.0285
wR2 = 0.0731
a
R1 ,wR2 b (all data) R1 = 0.0277
wR2 = 0.0673
Largest diff. peak
and hole (e/Å3)
0.636 and −0.757 0.456 and −0.411
2
aR = (||F0|−|FC||)/ |F0|. bwR = [ w(|F0|2−|FC|2)2/ w(F0 )]1/2
.
grid is composed of two 2,3-PDB opposite sides and two bib
opposites sides (Figure 3).
Description of the Crystal Structure
[Ni(2,5-PDB)(bib)0.5(H2O)2]n (2)
The coordination geometry of Ni(II) ion is a distorted oc-
tahedron completed by two oxygen atoms of two terminal-
coordination water molecules, two oxygen atoms from carboxy-
late groups, one nitrogen atom of pyridyl and one nitrogen atom
of the imidazole ring (Figure 4). Each carboxylate group adopts
monodentate coordination mode and connects the nickel(II) ions
FIG. 1. The coordination environment of Cd(II) ion. The hydrogen atoms are
omitted for clarity (color figure available online).

COORDINATION POLYMER
399
TABLE 2
Selected bond lengths (Å) and angles (◦) for complexes 1 and 2
Complex 1
Cd(1)—O(1)
Cd(1)—O(3)
2.314(3)
2.428(2)
123.63(6)
80.82(7)
70.11(9)
Cd(1)—N(1)
Cd(1)—N(2)i
2.309(2)
2.289(2)
N(2)i—Cd(1)—N(1)
N(2)i—Cd(1)—O(1)
N(1)—Cd(1)—O(1)
N(2)i—Cd(1)—O(3)
N(1)—Cd(1)—O(3)
85.78(8)
96.74(8)
Complex 2
Ni(1)—N(1)
Ni(1)—O(1w)
Ni(1)—O(3)
2.0311(14)
2.0467(14)
2.0661(13)
94.45(6)
90.94(6)
92.79(6)
92.39(7)
171.96(7)
91.33(6)
169.20(6)
87.86(6)
Ni(1)—(2w)
2.0708(14)
2.0838(14)
2.1279(13)
98.06(6)
88.72(6)
170.73(5)
86.12(6)
92.53(5)
78.40(5)
86.21(6)
Ni(1)—N(3)
Ni(1)—O(1)i
N(1)—Ni(1)—O(1w)
N(1)—Ni(1)—O(3)
O(1)W—Ni(1)—O(3)
N(1)—Ni(1)—O(2w)
O(1w)—Ni(1)—O(2w)
O(3)—Ni(1)—O(2w)
N(1)—Ni(1)—N(3)
O(1w)—Ni(1)—N(3)
N(1)—Ni(1)—O(1)i
O(1w)—Ni(1)—O(1)i
O(3)—Ni(1)—O(1)i
O(2w)—Ni(1)—O(1)i
N(3)—Ni(1)—O(1)i
O(3)—Ni(1)—N(3)
O(2w)—Ni(1)—N(3)
Symmetry code for compounds: (1): (i) x, –y + 1/2, z; (2) (i) –x + 2, –y + 1, –z + 1.
FIG. 2. The 1D chain constructed by carboxylate ligand along the c-axis (color figure available online).
TABLE 3
Parameters of Hydrogen-bonding Interactions in complex 2
Angle
. . .
D-H
. . . . . . . . .
d(D-H)/ d(H A)/ d(D A) (D-H A)
A
i
. . .
O1w-H1wa O4
0.87
0.87
0.88
0.88
2.01
1.97
2.15
1.93
2.709(2)
2.780(2)
2.830(2)
2.752(2)
136
154
134
155
ii
. . .
O1w-H1wb O2
iii
iv
. . .
O2w-H2wa O2
. . .
O2w-H1wb O4
Symmetry codes: (i) –x, 2 – y, 1 – z; (ii) –1 + x, y, z; (iii) x, –1 +
y, z; (iv) 1 – x, 1 – y, 1 – z.
FIG. 3. The 2D wave-like layer of 1 (color figure available online).

400
M. ZHANG AND F. GUO
to form 18-membered ring. The 18-membered rings are further
connected by the bib ligands to construct a one-dimensional
chain (Figure 5). In 2, each carboxylate group has one uncoordi-
nated carboxylate oxygen atom. As shown in Figure 6, the three-
dimensional supramolecular structure is formed via hydrogen
bonding interaction. The infinite chains [Ni(H2O)(2,5-PDB)]n
array uniformly in the 3D supramolecular architecture, which
possessed abundant hydrogen bonding interactions between
uncoordinated carboxylate oxygen atoms and coordinated
water molecules (Figure 6). The four kinds of hydrogen
bonds in the 3D supramolecular architecture are listed in
Table 3.
SUPPLEMENTARY MATERIALS
Crystallographic data for the structural analysis has been
deposited with the Cambridge Crystallographic Data Center,
CCDC reference numbers : 920498 & 920499.. These data can
be obtained free of charge at: http://www.ccdc.cam.ac.uk (or
FIG. 4. The coordination environment of Ni(II) ion. The hydrogen atoms are
omitted for clarity (color figure available online).
FIG. 5. The 1D chain formed by the bib ligands and 18-membered rings (color figure available online).
FIG. 6. The 3D supramolecular structure formed by the intermolecular bonding interactions (color figure available online).

COORDINATION POLYMER
401
Cambridge Crystallographic Data Center, 12 Union Road, Cam-
bridge CB2 1EZ, UK (fax: +44-1223-336-033; e-mail: deposit
@ ccdc.cam.ac.uk).
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