Solvothermal synthesis and structural characterization of a new one-dimensional coordination polymer [Zn(ATIBDC)DPA)] n (H 2TIBDC = 5-amino-2,4,6-triiodoisophthalic acid, DPA = 2,2′-dipyridylamine)

Article abstract of DOI:10.1134/S1070328411020011

A new one-dimensional (1D) zigzag chain coordination polymer [Zn(ATIBDC)(DPA)] _n (H₂ATIBDC = 5-amino-2,4,6- triiodoisophthalic acid, DPA = 2,2′-dipyridylamine) has been synthesized under solvothermal conditions and characterized by elemental analysis, IR, and single-crystal X-ray diffraction.

Full text of DOI:10.1134/S1070328411020011

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 3, pp. 176–179. © Pleiades Publishing, Ltd., 2011.
Solvothermal Synthesis and Structural Characterization
of a New OneꢀDimensional Coordination Polymer
[Zn(ATIBDC)DPA)]n (H2TIBDC = 5ꢀAminoꢀ2,4,6ꢀ
triiodoisophthalic Acid, DPA = 2,2'ꢀDipyridylamine)1
Y. E. Dua, L. Aib, and Z. B. Hana, *
a College of Chemistry, Liaoning University, Shenyang 110036, P.R. China
b College of Chemistry, Beijing Normal University, Beijing 100875, P.R. China
*Eꢀmail: ceshzb@lnu.edu.cn
Received May 21, 2010
Abstract—A new oneꢀdimensional (1D) zigzag chain coordination polymer [Zn(ATIBDC)(DPA)]n
(H2ATIBDC = 5ꢀaminoꢀ2,4,6ꢀtriiodoisophthalic acid, DPA = 2,2'ꢀdipyridylamine) has been synthesized
under solvothermal conditions and characterized by elemental analysis, IR, and singleꢀcrystal Xꢀray diffracꢀ
tion.
DOI: 10.1134/S1070328411020011
1
INTRODUCTION
EXPERIMENTAL
Materials and methods. All reagents and solvents
employed were commercially available and used as
received without further purification. The C, H, and N
microanalyses were carried out with a PerkinElmer
240 elemental analyzer. The FT IR spectra were
recorded from KBr pellets in the range 4000–400 cm–1
on a Nicolet 5DX spectrometer.
Solvothermal synthesis. A reaction mixture of
Zn(NO3)2 ⋅ 6H2O (0.059 g, 0.2 mmol), H2ATIBDC
(0.056 g, 0.1 mmol), DPA(0.034 g, 0.2 mmol) and
DMF–EtOH–H2O (v/v = 5 : 2 : 1,8 ml) was added to
a 23ꢀml Teflonꢀlined stainless steel autoclave, and
stirred at room temperature until the mixture became
Within the last decade, the rational design and synꢀ
thesis of metalꢀorganic frameworks (MOFs) have
received enormous interest in the area of coordination
chemistry and supramolecular chemistry, not only
because of their attractive variety of architectures and
topologies through the change of molecular building
blocks and reaction conditions, but also owing to their
practical or potential application as functional materiꢀ
als in catalysis, molecular recognition, ion exchange,
gas absorption, fluorescence, magnetic properties, etc.
[1–6]. However, it is still hard to rationally design the
MOFs with desired properties and esthetical structures
via the mixed ligands [7], because the selfꢀassembly
process is spontaneously generated from their compoꢀ
nent organic ligands and metal ions and influenced by
the sizes and shapes of the organic ligands [8–11].
Faced the challenge, inorganic chemists have done a
wonderful work in this field to identify packing trends
in view of the rational design of functional materials.
In recent years, plenty of selfꢀassembled coordination
polymers have been reported. However, only a few of
them are synthesized with 5ꢀaminoꢀ2,4,6ꢀtriiodoꢀ
isophthalic acid (H2ATIBDC) ligand [12]. In this
paper, we report the syntheses and crystal structures of
homogeneous. Then it was sealed and heated at 90
for three days followed by slow cooling to room temꢀ
perature at a rate of C/h. The resulting light colorless
block crystals of were obtained by filtration, washed
°C
5°
I
with distilled water and dried at ambient temperature
(the yield is ~57%).
For C18H11N4O4I3Zn
anal. calcd. (%):
C, 27.25;
C, 27.35;
N, 7.06;
N, 7.19;
H, 1.40.
H, 1.37.
Found (%):
[Zn(ATIBDC)(DPA)]n (I) (DPA = 2,2'ꢀdipyridyꢀ
lamine), which exhibits a new 1D zigzag chain strucꢀ
ture.
IR spectrum (ν
, cm–1): 3409 w, 3322 w, 1654 m,
1600 vs, 1481 s,*1340 s, 1159 m, 770 s, 491m.
Xꢀray crystal determination. Singleꢀcrystal Xꢀray difꢀ
fraction measurements were carried out on a Bruker
1
The article is published in the original.
176

SOLVOTHERMAL SYNTHESIS AND STRUCTURAL CHARACTERIZATION
177
Table 1. Crystallographic data and details of the experiment
P4 diffractometer at room temperature. The data colꢀ
lections were performed with MoKα radiation (
0.71073 Å) and a graphite monochromator using the
and refinement of structure
I
λ
=
ω
Parameter
Value
scan mode. The structure was solved by direct methods
and refined on F2 by fullꢀmatrix least squares using
SHELXTL [13–15]. The nonꢀhydrogen atoms were
treated anisotropically. Positions of hydrogen atoms
were generated geometrically. Crystallographic data
and experimental details for structural analyses are
summarized in Table 1, and the selected bond lengths
and angles are listed in Table 2. Hydrogen bonding
geometries are listed in Table 3.
Formula weight
Crystal system
793.38
Monoclinic
Space group
P21/n
Unit cell dimensions:
a
, Å
, Å
, Å
, deg
Å3
10.967(5)
15.658(8)
13.300(7)
91.719(7)
2284(2)
4
b
c
Supplementary material has been deposited with
the Cambridge Crystallographic Data Centre
(no. 789202; deposit@ccdc.cam.ac.uk or http://www.
ccdc.cam.ac.uk).
β
V
,
Z
ρcalcd, mg cm–3
Absorption coefficient, mm–1
(000)
Crystal size, nm
range, deg
Reflections collected
Independent reflections (Rint
, K
Parameters
Final indices (
indices (all data)
Largest diff. peak and hole,
2.308
RESULTS AND DISCUSSION
5.162
F
1472
Singleꢀcrystal Xꢀray diffraction analysis reveals
I crystallizes with an asymmetric unit including
one Zn(II) center, one ATIBDC ligand, and one DPA
ligand. As illustrated in Fig. 1, the Zn(II) center is fiveꢀ
coordinated by two nitrogen atoms from one
DPA ligand (Zn(1)–N(2) 2.029(8), Zn(1)–N(4)
2.065(9) Å) and three oxygen atoms from two individꢀ
that
0.36 × 0.27 × 0.21
θ
2.01 to 26.00
18639
)
4479 (0.2103)
293(2)
T
ual ATIBDC ligands (Zn(1)–O(4) 1.984(8), Zn(1–O(1
A)
271
2.037(7), Zn(1)–O(2 ) 2.393(9) . The coordinaꢀ
A
Å)
tion geometry around the Zn(II) center can be
described as a distorted trigonal bipyramid with the
bond angles ranging from 59.5(3)° (O(1A)Zn(1)O(2A))
R
I
> 2
σ
(
I
))*
R1 = 0.0664, wR2 = 0.1738
R
R
1 = 0.0846, wR2 = 0.2260
e
Å–3
2.359 and –4.575
to 148.8(3)° (N(4)Zn(1)O(2A)) (Table 2). The DPA
ligand coordinates to the Zn2+ ion in a bidentate
2
2
2
o
2
o
2
c
1/2
* R = Σ||F | – |F ||/Σ|F |; wR = Σ[w(F – F ) ]/Σ[w(F ) ]
.
1
o
c
o
2
chelating manner, while the ATIBDC ligand adopts
Table 2. Selected bond distances (Å) and angles (deg) for
I*
Bond
d
, Å
Bond
d, Å
Zn(1)–O(1)#1
Zn(1)–O(4)
Zn(1)–N(2)
2.037(7)
1.984(8)
2.029(8)
Zn(1)–N(4)
2.065(9)
2.393(3)
Zn(1)–O(2)#1
Angle
ω
, deg
Angle
ω, deg
O(4)Zn(1)N(2)
O(4)Zn(1)O(1)#1
N(2)Zn(1)O(1)#1
O(4)Zn(1)N(4)
119.3(3)
108.5(3)
125.9(3)
109.9(3)
92.3(3)
O(1)#1Zn(1)N(4)
O(4)Zn(1)O(2)#1
N(2)Zn(1)O(2)#1
O(1)#1Zn(1)O(2)#1
N(4)Zn(1)O(2) #1
94.1(3)
95.3(3)
91.1(3)
59.5(3)
148.8(3)
N(2) Zn(1)N(4)
#1
* Symmetry codes: x –1/2, –y – 1/2, z – 1/2.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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2011

178
DU et al.
Table 3. Geometric parameters of hydrogen bond of structure
Distance,
⋅⋅⋅ D⋅⋅⋅A
I
Å
Symmetry operations
for A atom
Contact D–H⋅⋅⋅
A
Angle D–H⋅⋅⋅A, deg
D–H
H
A
N(1)–H(1
N(1)–H(1
N(3)–H(3
A
)
⋅⋅⋅I(2)
0.86
0.86
0.86
0.93
2.72
2.78
1.95
2.36
3.203(10)
3.244(10)
2.803(12)
3.049(13)
117
115
174
131
x
,
,
y
,
,
z
z
B
)
⋅⋅⋅I(1)
x
y
A
)
⋅⋅⋅O(3)
–
x
+ 5/2,
y
+ 1/2, –
z + 3/2
C(9)–H(9
A
)
⋅⋅⋅O(2)
x
– 3/2, –
y
+ 1/2, z – 3/2
monodentate and bidentate chelating coordination 8.916(4) Å (Fig. 2). These chains are further linked via
mode to link two Zn2+ ions. The adjacent Zn(II) cenꢀ strong hydrogen bonds between carboxylate oxygen
ters are interconnected by ATIBDC ligands to form an atoms of ATIBDC ligands, uncoordinated nitrogen
infinite zigzag chain with a Zn⋅⋅⋅Zn distance of atoms, and
I
atoms (Table 3), forming a threeꢀdimenꢀ
O(2A)
C(10)
C(9)
O(1A)
I(2)
C(11)
N(2)
O(4)
N(1)
C(5)
Zn(1)
C(8)
C(4)
C(13)
N(4)
C(12)
N(3)
C(3)
C(6)
I(1)
O(3)
C(18)
C(7)
C(2)
C(14)
O(2)
I(3)
C(1)
C(15)
C(17)
C(16)
.
O(1)
Fig. 1. Coordination environment of the Zn(II) center in
I
O(3B
)
O(2C
)
O(3A)
O(1B)
O(2)
Zn(1
O(4
B
)
O(2D
)
O(1C)
A
)
O(4A)
O(1
A)
O(4
C
)
O(2
B
)
Zn(1
C
)
O(4)
Zn(1
B
)
O(2A)
O(4D)
O(1)
Zn(1)
O(1D
)
O(3
C
)
O(3)
O(3D)
Fig. 2. Fragment of zigzag 1D chain structure in
I.
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SOLVOTHERMAL SYNTHESIS AND STRUCTURAL CHARACTERIZATION
179
0
c
a
b
Fig. 3. View of the crystal packing along the y axis showing the hydrogen bonding interactions.
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sional supramolecular network (Fig. 3). The hydrogen
bonding interactions enhance the stability of the comꢀ
plex [16–18].
The IR spectrum of I not only shows the characterꢀ
istic bands of amino groups at 3409 cm–1 for the asymꢀ
metric stretching and at 3322 cm–1 for symmetric
stretching, but also illustrates the characteristic bands
of carboxyl groups at 1654, 1600 cm–1 for the asymꢀ
metric stretching and at 1481, 1340 cm–1 for symmetꢀ
ric stretching. The values of
Δ(νas–νs) are 173 and
,
260 cm–1 and = 173 and 200 cm–1, indicatꢀ
Δ
(
νas–νs)
ing that the coordination mode of one carboxyl group
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Chem. Eur. J., 2002, vol. 8, no. 9, p. 2026.
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Structure Refinement, Göttingen (Germany): Univ. of
Göttingen, 1997.
Δ(νas–
νs) = 260 cm–1 > 200 cm–1 demonstrates the
monodentate of the other carboxylic group to Zn(II)
[19]. The absence of strong characteristic peaks at
1700–1750 cm–1 reveals that all carboxylic groups are
completely deprotonated [20], which is consistent
with the results of the Xꢀray analysis.
,
14. Sheldrick, G.M., SHELXSꢀ97, Program for Crystal
Structure Solution, Göttingen (Germany): Univ. of
Göttingen, 1997
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ACKNOWLEDGMENTS
This work was supported by the National Nature
Science Fundational of China (grant no. 20871063).
16. Han, Z.B., He, Y.K., Ge, C.H., et al., Dalton Trans.
2007, no. 28, p. 3020.
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2011