A two-fold interpenetrated diamondlike 3D metal-organic Cd(II) complex based on 5-Iodo-isophthalic acid and 1,3-Bi(4-pyridyl)propane

Article abstract of DOI:10.5560/ZNB.2012-0065

A metal-organic framework based on 5-iodo-isophthalic acid (5-iipaH ₂) and the ancillary nitrogen ligand 1,3-bi(4- pyridyl)propane (bpp), namely [Cd(5-iipa)(bpp)(H₂O)]n (1), has been synthesized, and characterized by IR spectroscopy, elemental analysis, thermogravimetry, and X-ray crystallography. Complex 1 shows a two-fold interpenetrating 3D diamond-like architecture that is stabilized by hydrogen bonding, π ... π, I... π, and C-H... π interactions.

Full text of DOI:10.5560/ZNB.2012-0065

Note
499
A Two-fold Interpenetrated Diamond-
like 3D Metal-Organic Cd(II) Complex
Based on 5-Iodo-isophthalic Acid and
1,3-Bi(4-pyridyl)propane
mixture of multicarboxylate ligands and flexible N-
donor ligands has been used to generate a variety of
coordinating polymers under various reaction condi-
tion [16 – 21]. Recently, we chose 5-iodo-isophthalic
acid (5-iipaH2) and 1,3-bi(4-pyridyl)propane (bpp) as
ligands to construct novel architectures. Here we report
the new two-fold interpenetrating diamond-like 3D
metal-organic complex [Cd(5-iipa)(bpp)(H2O)]n (1).
Ming-Ming Dong, Deng-Yong Zhu, Yan Zhao,
Xiao-Yuan Li, and Shuang-Quan Zang
The College of Chemistry and Molecular Engineering,
Zhengzhou University, Zhengzhou 450001, P. R. China
Experimental Section
Reprint requests to Dr. Shuang-Quan Zang. Fax:
(+86)-371-6778 0136. E-mail: zangsqzg@zzu.edu.cn
Materials and general procedures
5-Iodo-isophthalic acid was prepared according to the lit-
erature [22]. All other starting materials were of analytical
grade and obtained from commercial sources and used with-
out further purification.
Z. Naturforsch. 2012, 67b, 499 – 503
DOI: 10.5560/ZNB.2012-0065
Received March 3, 2012
A metal-organic framework based on 5-iodo-isophthalic
acid (5-iipaH2) and the ancillary nitrogen ligand 1,3-bi(4-
pyridyl)propane (bpp), namely [Cd(5-iipa)(bpp)(H2O)]n (1),
has been synthesized, and characterized by IR spectroscopy,
elemental analysis, thermogravimetry, and X-ray crystallog-
raphy. Complex 1 shows a two-fold interpenetrating 3D
diamond-like architecture that is stabilized by hydrogen
bonding, π···π, I···π, and C−H···π interactions.
Synthesis of [Cd(5-iipa)(bpp)(H2O)]n (1)
Complex 1 was synthesized hydrothermally in a Teflon-
lined stainless-steel container by heating a mixture of
5-iodo-isophthalic acid (0.0146 g, 0.05 mmol), 1,3-bi(4-
pyridyl)propane (bpp) (0.01 g, 0.05 mmol), Cd(NO3)2 ·
4H2O (0.02 g, 0.05 mmol), KOH (0.006 g, 0.1 mmol), and
acetonitrile (0.5 mL) in 7 mL of distilled water at 160 ◦C
for 3 d. Subsequent cooling to room temperature yielded
colorless crystals of 1 (75% yield based on cadmium).
– C21H19CdIN2O5 (618.68): calcd. C 40.77, H 3.10, N,
4.53; found C 40.70, H 3.07, N 4.61. – IR (KBr, cm−1):
v = 3441(s), 2942(w), 1607(vs), 1560(m), 1424(s), 1398(m),
1347(s),1224(m), 819(m), 770(m), 715(s).
Key words: 5-Iodo-isophthalic Acid, Lattice
Interpenetration, Diamond-like Architecture,
Supramolecular Structure, Cadmium
Introduction
Physical measurements
The rational design and construction of coordination
polymers with interpenetrating structures have been an
increasingly active research area over recent years be-
cause many of such systems show an intriguing va-
riety of structures, useful properties and potential ap-
plications [1 – 5] A great number of architectures with
new topological types have been reported [6 – 9]. One
of the rational strategies to generate interpenetrating
structures is the judicious selection of suitable multi-
functional organic ligands and metal centers. It is well
known that multicarboxylate ligands [10] can influence
the structure of the coordination polymers by provid-
ing different coordination modes. Long organic spac-
ers such as 1,2-bis(4-pyridyl)ethane (bpe) [11, 12] and
1,3-bis(4-pyridyl)propane (bpp) [13 – 15] often show
diverse conformations in the self-assembly process and
have therefore proven to be good candidates to con-
Elemental analysis for C, H, and N was performed on
a Perkin-Elmer 240 elemental analyzer. The FT-IR spec-
tra were recorded from KBr pellets in the range from 4000
to 400 cm−1 on a Bruker VECTOR 22 spectrometer. Ther-
mal analysis was performed on a SDT 2960 thermal ana-
lyzer from room temperature to 800 ◦C at a heating rate of
20 ◦C min−1 under nitrogen flow.
X-Ray crystallography
A single crystal suitable for X-ray diffraction was
mounted on a Bruker SMART APEX CCD diffractome-
ter [23] The intensity data collection was carried out
using graphite-monochromatized MoKα radiation (λ =
˚
0.71073 A) at room temperature using the ω-scan technique.
Lorentz, polarization and absorption corrections were ap-
plied. The structure was solved by Direct Methods with
SHELXS-97 [24] and refined with full-matrix least-squares
struct uncommon interpenetrated architectures. The techniques using SHELXL-97 [25]. Anisotropic displacement
c
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Note
Table 1. Crystal data and numbers pertinent to data collection
and structure refinement of 1.
Compound
1
Formula
Mr
C21H19CdIN2O5
618.68
Crystal system
Space group
monoclinic
C2/c
˚
a, A
14.401(3)
19.253(4)
16.574(3)
102.91(3)
4479.2(2)
8
˚
b, A
˚
c, A
β, deg
3
˚
V, A
Z
Dcalcd., g cm−3
1.84
F(000), e
2400
hkl range
±17, ±22, ±19
22 330/3943/0.0353
281
0.0426/0.1317
0.0457/0.1351
0.0836/4.0421
1.088
Fig. 1 (color online). Metal coordination and atom labeling
in complex 1 (displacement ellipsoids at the 50% probability
level; all hydrogen atoms are omitted for clarity).
Reflections collected/independent/Rint
Refined parameters
R1/wR2 (I > 2σ(I))a, b
R1/wR2 (all data)a, b
Weighting scheme A/Bb
GOFc
−3
˚
∆ρfin (max/min), e A
0.41/−0.52
a
R1 = Σ k Fok−kF k /ΣkFok;
c
b
wR2 = [Σw(Fo2 − F2)2/Σw(Fo2)2]1/2, w = [σ2(Fo2) + (AP)2 +
c
BP]−1, where P = (Max(Fo2,0)+2F2)/3;
c
c
GoF = [Σw(Fo2 −F2)2/(nobs −nparam)]1/2
.
c
parameters were assigned to all non-hydrogen atoms. An-
alytical expressions of neutral atom scattering factors were
employed, and anomalous dispersion corrections were incor-
porated. I1 in 1 has two disordered positions with occupancy
ratios of 0.43 : 0.56. The crystallographic data and selected
bond lengths and angles for 1 are listed in Tables 1 and 2.
CCDC 778217 contains the supplementary crystallo-
graphic data for this paper. The data can be obtained free
of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data request/cif.
Fig. 2 (color online). A view of the [Cd(iipa)]n chain running
along the crystallographic c axis.
bpp ligand. The Cd(II) center is coordinated by two
O atoms from two different 5-iipa2− ligands [O(2),
O(3A)], two pyridyl nitrogen atoms from different bpp
ligands and one water oxygen atom to form a dis-
torted trigonal-bipyramidal environment. Furthermore,
an additional oxygen atom of the 5-iipa2− ligand
is coordinated in an albeit longer and weaker bond
Results and Discussions
˚
(Cd(1)−O(1) 2.634(4) A).
The bpp ligand adopts the TG conformation, with
Structure description of [Cd(5-iipa)(bpp)(H2O)]n (1)
˚
an N···N distance of 8.336 A and a dihedral angle of
As is shown in Fig. 1, the asymmetric unit of 1 con- 86.6 ◦C between the two pyridyl rings. The 5-iipa2−
tains one Cd dication, one 5-iipa2− dianion and one ligand acts as a bridge with one carboxylate group
Table 2. Selected bond
Cd(1)−O(3A)
2.230(4) Cd(1)−O(2)
2.361(4) Cd(1)−N(2B)
2.241(4) Cd(1)−N(1)
2.376(4) Cd(1)−O(1)
2.287(4)
2.634(4)
139.3(1)
˚
lengths (A) and angles
Cd(1)−O(1W)
(deg) for 1a.
O(3A)−Cd(1)−O(2)
131.1(2) O(3A)−Cd(1)−N(1) 89.6(2)
O(2)−Cd(1)−N(1)
O(3A)−Cd(1)−O(1W) 80.7(2)
O(3A)−Cd(1)−N(2B) 91.5(2)
O(2)−Cd(1)−O(1W) 88.7(1)
O(2)−Cd(1)−N(2B) 88.9(2)
N(1)−Cd(1)−O(1W) 96.5(1)
N(1)−Cd(1)−N(2B) 93.5(2)
O(1W)−Cd(1)−O(1) 98.3(1)
O(2)−Cd(1)−O(1)
N(2B)−Cd(1)−O(1)
52.7(1)
90.2(1)
N(1)−Cd(1)−O(1)
86.6(1)
a
Symmetry codes: A: x, −y, z+1/2; B: x−1/2, −y+1/2, z−1/2.
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Fig. 3 (color online). a) One
set of the 3D framework
(one segment is highlighted
in orange); b) schematic
view of the diamond-like
net (one fragment is high-
lighted in turquiose).
Fig. 4 (color online). a)
Space-filling diagram of
the interpenetrating 3D
framework; b) the different
non-covalent interactions
in the architecture. (a and b
represent the π···π stacking
between pyridine rings and
phenyl rings, respectively).
˚
[C(7)] in a monodentate and the other [C(8)] in an un- which contains the N2 atom: 2.952 A] suggest that
symmetrical chelating bidentate fashion linking the Cd there are face-to-face π···π stacking and C−H···π in-
atoms to form a zig-zag chain (Fig. 2). Each chain is teractions. H1WA and H1WB are hydrogen bonded
connected to four other such chains through bpp lig- to O2 and O4 atoms, respectively, which come from
ands to yield a 3D framework, as shown in Fig. 3a. If
the Cd center is considered as a four-connected node
(connecting to four other Cd centers via two 5-iipa2−
and two bpp ligands), the 3D structure of 1 can be clas-
sified as a diamond-type (6, 4) net with a (66) Schla¨fli
symbol (Fig. 3b) [26].
The presence of the large voids (ca. 18.00 ×
2
˚
6.69 A ) opens up the way for the existence of inter-
penetration, and two sets of such 3D frameworks are
interlaced in a parallel fashion to give rise to a two-fold
interpenetrated architecture (Fig. 4a). Further investi-
gation of this structure has indicated that different non-
covalent interactions can be detected between the two
sets of 3D frameworks, as shown in Fig. 4b. The short
distances between neighboring aromatic rings which
belong to different motifs [centroid-centroid distance
˚
3.714 A between the pyridine rings which contain the
˚
N1 atom, and 3.609 A between the phenyl ring which
contains C1−C6; H10−center of the pyridine ring pound 1.
Fig. 5. Thermogravimetric analysis (TGA) curve for com-
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502
Note
˚
another set of the framework, (O1W−O4C, 2.69 A; of complex 1 in the solid state was investigated at
˚
O1W−O2D, 2.89 A; symmetry codes: C −x + 1, y, room temperature. However, the compound presents
−z−1/2; D −x+1, −y, −z). The two-fold interpene- only very weak photoluminescence. The reason for this
trated architecture is stabilized by these different non- phenomenon may be the heavy-atom effect [28].
˚
covalent interactions. The distance of 3.847 A between
I1 and the nearest edge (C20 – C21) of an aromatic ring
which comes from another motif suggests that there
are weak I···π interactions [27] which also contribute
to the formation of the structure.
Conclusion
In this study, we have synthesized and characterized
a novel Cd(II) coordination polymer based on the 5-
iipa2− ligand and the N,N0-type ligand bpp. The com-
plex features a two-fold interpenetrating diamond-like
3D metal-organic framework. The result shows that the
mixture of the rigid multicarboxylate ligand and the
flexible N-containing ligand should further be consid-
ered in the design of intriguing architectures, and our
future research will therefore focus on interpenetrated
coordination polymers with potential functionalities by
using different ligands and metal ions.
Thermogravimetric analysis
Thermogravimetric analysis (TGA) of complex 1
was performed to study its thermal stability. The TGA
curve is shown in Fig. 5. The weight loss of the
coordinated water molecules occurs in the range of
128 – 176 ◦C (observed, 2.90%; calculated, 2.91%).
The decomposition of the anhydrous compound begins
at 210 ◦C.
Acknowledgement
Luminescence properties
We gratefully acknowledge financial support by the Na-
tional Natural Science Foundation of China (no. 20901070)
Considering that some Cd(II) complexes have excel-
lent luminescence properties, the photoluminescence and Zhengzhou University (P. R. China).
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