Syntheses, structures, and properties of CdII and Co II complexes with 5-(pyridin-4-yl)isophthalate

Article abstract of DOI:10.1080/00958972.2012.742890

A N-donor containing carboxylic ligand, 5-(pyridin-4-yl)isophthalic acid (H₂L), was applied to construct two new coordination polymers [Cd(L)(DMF)]_n (1, DMF=N,N-dimethylformamide) and {[Co(L)(H ₂O)₂] · 0.5CH

Full text of DOI:10.1080/00958972.2012.742890

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Syntheses, structures, and properties
II
II
of Cd and Co complexes with 5-
(
pyridin-4-yl)isophthalate
a a b
a
Chao Hou , Yue Zhao , Taka-Aki Okamura , Peng Wang
&
a
Wei-Yin Sun
a
Coordination Chemistry Institute, State Key Laboratory of
Coordination Chemistry, School of Chemistry and Chemical
Engineering, Nanjing National Laboratory of Microstructures,
Nanjing University , Nanjing 210093 , China
b
Department of Macromolecular Science , Graduate School of
Science, Osaka University , Toyonaka , Osaka 560-0043 , Japan
Accepted author version posted online: 24 Oct 2012.Published
online: 16 Nov 2012.
To cite this article: Chao Hou , Yue Zhao , Taka-Aki Okamura , Peng Wang & Wei-Yin Sun (2012)
II
II
Syntheses, structures, and properties of Cd and Co complexes with 5-(pyridin-4-yl)isophthalate,
Journal of Coordination Chemistry, 65:24, 4409-4418, DOI: 10.1080/00958972.2012.742890
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Journal of Coordination Chemistry
Vol. 65, No. 24, 20 December 2012, 4409–4418
II
II
Syntheses, structures, and properties of Cd and Co complexes
with 5-(pyridin-4-yl)isophthalate
CHAO HOUy, YUE ZHAOy, TAKA-AKI OKAMURAz, PENG WANGy
and WEI-YIN SUN*y
yCoordination Chemistry Institute, State Key Laboratory of Coordination Chemistry,
School of Chemistry and Chemical Engineering, Nanjing National Laboratory of
Microstructures, Nanjing University, Nanjing 210093, China
zDepartment of Macromolecular Science, Graduate School of Science, Osaka University,
Toyonaka, Osaka 560-0043, Japan
(
Received 31 July 2012; in final form 11 October 2012)
A N-donor containing carboxylic ligand, 5-(pyridin-4-yl)isophthalic acid (H
construct two new coordination polymers [Cd(L)(DMF)]
(1, DMF ¼ N,N-dimethylformamide)
and {[Co(L)(H O) OH ꢀ 1.5H O} (2) under different conditions. The complexes were
] ꢀ 0.5CH
characterized by IR, elemental, and thermogravimetric analyses, powder and single crystal X-ray
2
L), was applied to
n
2
2
3
2
n
2
ꢁ
II
2ꢁ
diffraction. In 1 each L links four Cd to form a 3-D framework, while in 2 each L connects
three metals to form a 2-D layer structure, which is further connected together by hydrogen
bonds to form a 3-D architecture. The thermal stability of the complexes and the
photoluminescence of 1 were investigated.
II
II
Keywords: Cd complex; Co complex; Crystal structure; Photoluminescence
1. Introduction
Coordination polymers or metal–organic frameworks (MOFs) have received attention
for intriguing architectures and topologies, and potential applications in gas storage/
separation, catalysis, magnetism, photoluminescence, etc. [1, 2]. Most studies have
focused on the design and construction of MOFs and attempts to develop structure–
property relationships [2, 3]. However, obtaining desired architectures of MOFs
constructed by organic ligands and metal salts is still a long-term challenge to chemists;
assembly is complicated and minor changes in the chemical environment, reaction
temperature, pH, solvent, counterions, etc., can have subtle but important influence on
the formation and structure of the complexes [4–7]. Carefully selected organic ligands
have a decisive role in the construction of MOFs.
Carboxylates are of special interest because of their variable coordination modes such
as terminal monodentate, chelating, bridging bidentate, bridging tridentate [8], and also
*
Corresponding author. Email: sunwy@nju.edu.cn
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ß 2012 Taylor & Francis
http://dx.doi.org/10.1080/00958972.2012.742890

4
410
C. Hou et al.
because of their ability to act as hydrogen bond acceptors and donors to assemble
supramolecular structures [9]. N-donor ligands such as 1,3,5-tris(1-imidazolyl)benzene,
0
3
,4 -bipyridine and 1,3-bis(4-pyridyl)propane are widely used for constructing
coordination complexes [10–12]. The application of these N-donor ligands in the
MOFs synthesis often results in structures with unique motifs and interesting
properties [11–13].
Based on the above arguments, in this work we employed a carboxylate- and pyridyl-
containing ligand, 5-(pyridin-4-yl)isophthalic acid (H L), which has remarkable
2
features as follows: (a) it is a rigid ligand which may favor the construction of
coordination architectures with high thermal stability; (b) the carboxylate can have
different coordination modes to satisfy the coordination geometric requirement of
metal centers; and (c) the ligand can offer additional hydrogen bonding to consolidate
the structure. Only a small number of MOFs based on this ligand has been reported
hitherto, thus it is necessary to enrich the variety of 5-(pyridin-4-yl)isophthalate-based
MOFs [14]. Herein we report the syntheses and crystal structures of two new
2
ꢁ
complexes based on L , [Cd(L)(DMF)] (1, DMF ¼ N,N-dimethylformamide) and
n
{
[Co(L)(H O) ] ꢀ 0.5CH OH ꢀ 1.5H O} (2). They are also characterized by IR,
2
2
3
2
n
elemental, and thermogravimetric analyses (TGA), powder and single crystal X-ray
diffractions, and the luminescence of 1 has been studied.
2
2
. Experimental
.1. Materials and methods
All commercially available chemicals and solvents are of reagent grade and used as
received. H L was synthesized according to the literature [14a]. Elemental analyses for
2
C, H, and N were performed on a Perkin-Elmer 240C Elemental Analyzer at the
analysis center of Nanjing University. TGA were performed on a simultaneous SDT
ꢂ
ꢁ1
2
960 thermal analyzer under nitrogen with a heating rate of 10 C min . FT-IR spectra
ꢁ
1
were recorded from 400 to 4000 cm on a Bruker Vector22 FT-IR spectrophotometer
using KBr pellets. Powder X-ray diffraction (PXRD) measurements were performed on
˚
a Bruker D8 Advance X-ray diffractometer using Cu-Ka radiation (ꢀ ¼ 1.5418 A), in
which the X-ray tube was operated at 40 kV and 40 mA at room temperature.
Luminescence spectra for the powdered solid samples were measured on an Aminco
Bowman Series 2 spectrofluorometer with a xenon arc lamp as the light source. In
measurements of emission and excitation spectra the pass width is 5 nm, and all the
measurements were carried out under the same experimental conditions.
2
2
.2. Syntheses of complexes
.2.1. [Cd(L)(DMF)] (1). A mixture of Cd(NO ) ꢀ 4H O (15.4 mg, 0.05 mmol), H L
n
3 2
2
2
(12.2 mg, 0.05 mmol), concentrated hydrochloric acid (50 mL), and DMF (3 mL) was
treated by ultrasonic vibration. The mixture was then sealed into a Teflon-lined
ꢂ
stainless steel container and heated at 120 C for 3 days. After cooling to room
temperature, colorless block crystals of 1 were obtained in 54% yield. Anal. Calcd for

5
-(Pyridin-4-yl)isophthalate
4411
C H CdN O (%): C, 45.04; H, 3.31; N, 6.57. Found (%): C, 44.99; H, 3.29; N, 6.54.
1
6
14
2
5
ꢁ
1
IR (KBr pellet, cm ): 3424 (s), 1658 (s), 1616 (s), 1571 (s), 1442 (m), 1416 (m), 1358 (s),
1
292 (w), 1217 (w), 1099 (w), 777 (w), 729 (m), 644 (w), 506 (w).
2
layering method. A buffer layer of a CH OH : H O (1 : 1) solution (8 mL) was carefully
.2.2. {[Co(L)(H O) ]
.
0.5CH OH 1.5H O} (2). Compound 2 was prepared by the
2 n
.
2
2
3
3
2
layered over a solution of H L (24.3 mg, 0.1 mmol) and KOH (11.2 mg, 0.2 mmol) in
2
H O (3 mL). Then a solution of Co(NO ) ꢀ 6H O (29.2 mg, 0.1 mmol) in CH OH
2
3 2
2
3
(3 mL) was layered over the buffer layer. Block reddish-purple crystals of 2 were
obtained after 2 months in 42% yield. Anal. Calcd for C13.50H CoNO (%): C, 42.76;
16
8
ꢁ
1
H, 4.26; N, 3.69. Found (%): C, 43.12; H, 4.17; N, 3.72. IR (KBr pellet, cm ): 3416 (s),
614 (s), 1558 (s), 1508 (m), 1446 (s), 1374 (s), 1235 (w), 1074 (w), 1024 (w), 777 (m), 734
m), 647 (m).
1
(
2
.3. X-ray structure determination
Structural data for 1 were collected on a Bruker Smart Apex CCD with graphite-
˚
monochromated Mo-Ka radiation (ꢀ ¼ 0.71073 A) at 293(2) K. The structure was
solved by direct methods and refined with full-matrix least-squares using the SHELXS-
97 and SHELXL-97 programs [15]. The non-hydrogen atoms were refined anisotrop-
ically. Hydrogen atoms of ligands were generated geometrically. For C102 and C103 in
1, the locations of difference Fourier peaks suggested disorder in which two orientations
ꢂ
of the methyl were rotated by 60 relative to each other. The single X-ray diffraction
measurements for 2 were made on a Rigaku Rapid II imaging plate area detector with
˚
Mo-Ka radiation (0.71075 A) using MicroMax-007HF microfocus rotating anode
X-ray generator and VariMax-Mo optics at 200 K. The structure of 2 was solved by
direct methods with SIR92 and expanded using Fourier techniques by DIRFID-99 [16].
The non-hydrogen atoms were refined anisotropically. Hydrogen atoms of water with
O5, O6, and O8 were located directly; hydrogen atoms of water and methanol with O7
and O21 were not found, while all the other hydrogen atoms were generated
geometrically and refined isotropically using the riding model. All calculations for 2
were performed using the CrystalStructure crystallographic software package except for
refinement, which was performed using SHELXL-97 [17]. The details of the crystal
parameters, data collection, and refinement for the complexes are summarized in table 1
and selected bond lengths and angles are listed in table 2.
3
3
. Results and discussion
.1. Description of the crystal structure of 1
II
2ꢁ
The asymmetric unit of 1 consists of one Cd , one L , and one coordinated DMF. As
depicted in figure 1(a), Cd1 is seven-coordinate with a pentagonal bipyramid
coordination geometry by one nitrogen (N11A) and one oxygen (O1C) atoms from
2
ꢁ
two different L , two pairs of oxygen atoms (O1B, O2B and O3, O4) from another two
2
distinct L , respectively, and one oxygen atom (O101) from coordinated DMF. Each
ꢁ

4
412
C. Hou et al.
Table 1. Crystallographic data and structure refinement details for 1 and 2.
1
2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C
426.69
293(2)
Monoclinic
16
H
14CdN
2
O
5
C
13.50
H
16CoNO
8
379.20
200
Triclinic
P2
1
/c
P1ꢀ
˚
ꢂ
)
Unit cell dimensions (A,
a
b
c
ꢁ
ꢂ
ꢃ
9.238(5)
18.225(9)
9.743(5)
90.00
104.940(9)
90.00
1584.9(14), 4
1.788
1.407
848
8466
8.967(4)
10.165(4)
10.213(5)
115.635(15)
90.746(18)
110.684(18)
769.8(6), 2
1.636
1.157
390
5805
2698
3
˚
Volume (A ), Z
Calculated density (g cm
Absorption coefficient (mm
F(000)
Reflections collected
Independent reflection
Goodness-of-fit on F
Final R indices [I 4 2ꢄ(I)]
R indices (all data)
ꢁ
3
)
1
ꢁ
)
3264
1.199
2
1.230
a,b
R
R
1
1
¼ 0.0517, wR
2
2
¼ 0.1085
¼ 0.1117
R
R
1
1
¼ 0.0698, wR
2
2
¼ 0.1884
¼ 0.1889
¼ 0.0607, wR
¼ 0.0712, wR
a
R
wR
1
¼ ÆF
o
ꢁ F
c o
/ÆF .
b
2
2
21/2
2
2
o
2
2
o
2
c
2
¼ Æw(F ꢁ F )/Æw(F
o
c
o
)
, where w ¼ 1/[ꢄ (F ) þ (aP) þ bP]; P ¼ (F þ 2F )/3.
˚
Table 2. Selected bond lengths (A) and bond angles ( ) for 1 and 2.
ꢂ
a
1
Cd1–N11A
Cd1–O101
Cd1–O1C
Cd1–O3
2.299(4)
2.375(5)
2.396(4)
2.531(4)
Cd1–O4
Cd1–O2B
Cd1–O1B
2.302(4)
2.382(4)
2.494(4)
N11A–Cd1–O4
O4–Cd1–O101
O4–Cd1–O2B
N11A–Cd1–O1C
O101–Cd1–O1C
N11A–Cd1–O1B
O101–Cd1–O1B
O1C–Cd1–O1B
O4–Cd1–O3
135.12(14)
86.30(16)
137.08(13)
97.22(15)
170.75(17)
137.13(13)
94.96(17)
76.09(13)
53.83(13)
160.29(15)
141.46(12)
N11A–Cd1–O101
N11A–Cd1–O2B
O101–Cd1–O2B
O4–Cd1–O1C
O2B–Cd1–O1C
O4–Cd1–O1B
O2B–Cd1–O1B
N11A–Cd1–O3
O101–Cd1–O3
O1C–Cd1–O3
90.95(18)
85.85(14)
79.76(16)
90.95(14)
96.43(13)
87.69(12)
53.85(13)
81.29(14)
85.55(17)
99.94(14)
O2B–Cd1–O3
O1B–Cd1–O3
2
Co1–N11A
Co1–O3B
Co1–O1
2.099(6)
2.058(5)
2.186(5)
Co1–O5
Co1–O6
Co1–O2
2.093(6)
2.109(6)
2.221(5)
O3B–Co1–O5
O5–Co1–N11A
O5–Co1–O6
O3B–Co1–O1
N11A–Co1–O1
O3B–Co1–O2
N11A–Co1–O2
O1–Co1–O2
86.5(2)
96.2(2)
174.3(2)
96.0(2)
148.1(2)
155.27(19)
89.5(2)
O3B–Co1–N11A
O3B–Co1–O6
N11A–Co1–O6
O5–Co1–O1
O6–Co1–O1
O5–Co1–O2
O6–Co1–O2
115.2(2)
90.1(2)
89.3(2)
91.5(2)
84.3(2)
89.0(2)
92.2(2)
59.75(19)
a
Symmetry transformations used to generate equivalent atoms: A: x ꢁ 1, y, z ꢁ 1; B: ꢁx, y ꢁ 1/2, ꢁz þ 3/2; C: x, ꢁy þ 1/2,
z ꢁ 1/2 for 1; A: x ꢁ 1, y ꢁ 1, z ꢁ 1; B: x, y, z ꢁ 1 for 2.

5
-(Pyridin-4-yl)isophthalate
4413
Figure 1. (a) Coordination environment of Cd1 in 1 with the ellipsoids drawn at the 30% probability level.
Hydrogen atoms are omitted for clarity. (b) The 2-D layer structure of 1 formed by neglecting the pyridines of
2
ꢁ
. (c) The 3-D framework of 1. (d) Schematic representation of the (3,6)-connected 2-nodal 3-D network of
L
1
2
2
10
3
2
with (4.6 ) (4 .6 .8 ) topology.
2
ꢁ
II
in 1 is a ꢅ -bridge to link four Cd (mode A, scheme 1): the pyridine nitrogen links
L
the first Cd , one ꢅ -ꢆ :ꢆ carboxylate connects two Cd and the other ꢅ -ꢆ : ꢆ
4
II
2
1
II
1
1
2
1
II
carboxylate ligates the fourth one. Two adjacent Cd are connected by two ꢅ -ꢆ :ꢆ
2
1
2
˚
carboxylates to form a dimeric unit with a Cdꢀ ꢀ ꢀCd separation of 3.85 A. If the

4
414
C. Hou et al.
2
Scheme 1. Coordination modes of L in 1 and 2.
ꢁ
2
ꢁ
II
coordination of pyridine of L is neglected, the Cd centers are bridged by carboxylates
2
ꢁ
of L to give a 2-D network in the bc plane, as illustrated in figure 1(b). Then the layers
are further linked by the pyridine groups to generate a 3-D framework (figure 1c).
To further understand the structure of 1, topological analysis by reducing
multidimensional structure to simple node-and-linker net was performed. Based on
2
ꢁ
the simplification principle [18], each dimeric unit connects six L , which can be viewed
ꢁ
2
as a six-connector. Meanwhile, each L can be regarded as a three-connected node
II
since it links three dimeric Cd units. Hence, the overall structure of 1 is a (3,6)-
connected 2-nodal 3-D net with stoichiometry (3–c) (6–c), as shown in figure 1(d).
2
Topology analysis by TOPOS suggests that the Point (Schla
¨
fli) symbol of the net is
2
4.6 ) (4 .6 .8 ) [19].
2
10
3
(
2
3
.2. Description of the crystal structure of 2
ꢀ
Single crystal X-ray diffraction analysis revealed that 2 crystallizes in the triclinic P1
II
2ꢁ
space group. In the asymmetric unit of 2, there are one Co , one L , two coordinated
water molecules, 0.5 free methanols, and 1.5 free water molecules. As depicted in
figure 2(a), each Co1 is six-coordinate with distorted octahedral coordination geometry
2
ꢁ
by one oxygen (O3B) and one nitrogen (N11A) atoms from two distinct L , two
2
oxygen atoms (O1, O2) from another L forming the equatorial plane, and two water
ꢁ
2
molecules (O5, O6) at an apical position. L in 2 adopts the coordination mode B
ꢁ
II
1
scheme 1) as a ꢅ -bridge linking three Co through the pyridine nitrogen, one ꢅ -ꢆ : ꢆ
0
(
carboxylate and a ꢅ -ꢆ : ꢆ one. Therefore, Co are connected by L to form a 2-D
3
1
1
1
II
2ꢁ
1
network with large meshes filled with free water and methanol (figure 2b). The layers
are linked by hydrogen bonds to generate a 3-D structure (figure 2c). The hydrogen
bonding data are summarized in table S1.
3
.3. Comparison of the structures
Complexes 1 and 2 have 3-D and 2-D framework structures with different topologies
vide supra), which can be ascribed to the different coordination numbers and
(
II
II
geometries of Cd and Co as well as the different coordination modes of the ligand
scheme 1). Previously reported metal complexes with phthalate or isophthalate
(

5
-(Pyridin-4-yl)isophthalate
4415
II
Figure 2. (a) Coordination environment of Co in 2 with the ellipsoids drawn at the 30% probability level.
Hydrogen atoms, free water, and methanol are omitted for clarity. (b) The 2-D layer structure of 2 with water
molecules and methanols encapsulated inside large meshes. Hydrogen atoms are omitted for clarity. (c) The
3-D structure of 2 formed by hydrogen bonds, indicated by dashed lines.
derivatives also show diverse structures and topologies [20]. The results of present and
previous studies [8, 9, 20] imply that the multicarboxylate ligands are powerful and
important in the construction of MOFs.
3.4. PXRD and thermal stabilities
The phase purity of bulk products of the complexes was further confirmed by PXRD,
and each PXRD pattern of the as-synthesized sample is consistent with the simulated
one, as illustrated in figure S1.
TGA were carried out for 1 and 2 and the results of the TGA are shown in figure S2.
ꢂ
Complex 1 shows a weight loss of 17.41% (Calcd 17.13%) before 285 C, which

4
416
C. Hou et al.
H2L
Complex 1
350
400
450
500
Wavelength/nm
2
Figure 3. Emission spectra of H L and 1 in the solid state at room temperature.
ꢂ
corresponds to release of coordinated DMF; the residue is stable up to ca 380 C.
ꢂ
Complex 2 shows a weight loss of 19.21% (Calcd 20.83%) before 335 C, which
corresponds to the release of methanol, free and coordinated water.
3
.5. Photoluminescence property of 1
1
Inorganic–organic hybrid coordination polymers with d metal centers have been
0
investigated for fluorescence [21]. Fluorescence emission spectra of H L and 1 were
2
measured in the solid state at room temperature (figure 3). Upon excitation at 350 nm,
free H L exhibits maximum emission at 384 nm and 1 shows similar emission at 427 nm.
2
Thus, the emission band of 1 should be ascribed to intraligand ꢇ–ꢇ* transition [21]. The
observed red shift of the emission maximum between 1 and H L originates from
coordination interactions between the metal and ligand [22].
2
4
. Conclusion
Two new coordination complexes with distinct architectures based on H L,
2
[
Cd(L)(DMF)] (1), and {[Co(L)(H O) ] ꢀ 0.5CH OH ꢀ 1.5H O} (2), have been con-
n
2
2
3
2
n
structed and structurally characterized. Photoluminescence of 1 is investigated. The
results suggest that it is a useful strategy to employ carboxylate- and pyridyl-containing
ligands to design and synthesize MOFs with intriguing architecture and properties.
Supplementary material
Crystallographic data for the structures reported in this article have been deposited with
the Cambridge Crystallographic Data Centre as Supplementary Publication
No. CCDC-894153 (1) and 894154 (2). Copies of the data can be obtained at http://
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK; Fax: þ44 1 223 336 033; Email: deposit@ccdc.cam.ac.uk).

5
-(Pyridin-4-yl)isophthalate
4417
Acknowledgments
This work was financially supported by the National Natural Science Foundation of
China (Grant no. 91122001 and 21021062) and the National Basic Research Program of
China (Grant no. 2010CB923303).
References
[
´
1] (a) D.J. Tranchemontagne, J.L. Mendoza-Cortes, M. O’Keeffe, O.M. Yaghi. Chem. Soc. Rev., 38, 1257
2009); (b) N.L. Rosi, J. Kim, M. Eddaoudi, B. Chen, M. O’Keeffe, O.M. Yaghi. J. Am. Chem. Soc., 127,
(
1504 (2005); (c) Z. Su, Z.-S. Bai, J. Xu, T. Okamura, G.-X. Liu, Q. Chu, X.-F. Wang, W.-Y. Sun,
N. Ueyama. CrystEngComm, 11, 873 (2009); (d) G.-Z. Liu, L.-Y. Xin, L.-Y. Wang. CrystEngComm,
3, 3013 (2011); (e) Y. Liu, K. Li, S.-C. Wei, M. Pan, C.-Y. Su. CrystEngComm, 13, 4564 (2011).
2] (a) S.-S. Chen, M. Chen, S. Takamizawa, P. Wang, G.-C. Lv, W.-Y. Sun. Chem. Commun., 47, 4902
2011); (b) B. Li, Z. Zhang, Y. Li, K. Yao, Y. Zhu, Z. Deng, F. Yang, X. Zhou, G. Li, H. Wu, N. Nijem,
1
[
(
Y.J. Chabal, Z. Lai, Y. Han, Z. Shi, S. Feng, J. Li. Angew. Chem. Int. Ed., 51, 1412 (2012); (c) L. Ma,
J.M. Falkowski, C. Abney, W. Lin. Nat. Chem., 2, 838 (2010); (d) Q.-Y. Liu, Y.-L. Wang, Z.-M. Shan,
R. Cao, Y.-L. Jiang, Z.-J. Wang, E.-L. Yang. Inorg. Chem., 49, 8191 (2010); (e) Y.-Q. Wang, W.-W. Sun,
Z.-D. Wang, Q.-X. Jia, E.-Q. Gao, Y. Song. Chem. Commun., 47, 6386 (2011).
[
3] (a) C. Hou, Q. Liu, Y. Lu, T. Okamura, P. Wang, M. Chen, W.-Y. Sun. Microporous Mesoporous
Mater., 152, 96 (2012); (b) K.L. Gurunatha, K. Uemura, T.K. Maji. Inorg. Chem., 47, 6578 (2008);
(
(
c) Y.-B. Zhang, W.-X. Zhang, F.-Y. Feng, J.-P. Zhang, X.-M. Chen. Angew. Chem. Int. Ed., 48, 5287
2009); (d) Z. Su, M. Chen, T. Okamura, M.-S. Chen, S.-S. Chen, W.-Y. Sun. Inorg. Chem., 50,
9
7
85 (2011); (e) S.-S. Chen, M. Chen, S. Takamizawa, M.-S. Chen, Z. Su, W.-Y. Sun. Chem. Commun., 47,
52 (2011).
[
[
4] (a) D. Sun, Y. Ke, T.M. Mattox, B.A. Ooro, H.-C. Zhou. Chem. Commun., 5447 (2005); (b) L.-F. Ma,
L.-Y. Wang, D.-H. Lu, S.R. Batten, J.-G. Wang. Cryst. Growth Des., 9, 1741 (2009).
5] (a) Z. Su, J. Fan, T. Okamura, W.-Y. Sun, N. Ueyama. Cryst. Growth Des., 10, 3515 (2010); (b) S.-T.
Wu, L.-S. Long, R.-B. Huang, L.-S. Zheng. Cryst. Growth Des., 7, 1746 (2007).
[
[
[
6] S.R. Halper, L. Do, J.R. Stork, S.M. Cohen. J. Am. Chem. Soc., 128, 15255 (2006).
7] X.-C. Huang, J.-P. Zhang, Y.-Y. Lin, X.-M. Chen. Chem. Commun., 2232 (2005).
8] (a) M. Hu, M. Chen, X.-G. Yang, S.M. Fang, C.-S. Liu. J. Coord. Chem., 64, 3928 (2011); (b) J.-C. Dai,
X.-T. Wu, Z.-Y. Fu, C.-P. Cui, S.-M. Hu, W.-X. Du, L.-M. Wu, H.-H. Zhang, R.-Q. Sun. Inorg. Chem.,
41, 1391 (2002).
[
9] (a) A.P.S. Pannu, P. Kapoor, G. Hundal, R. Kapoor, M. Martinez-Ripoll, M.S. Hundal. J. Coord.
Chem., 64, 1566 (2011); (b) Z. Su, Z.-B. Wang, W.-Y. Sun. J. Coord. Chem., 64, 70 (2011).
[
[
10] Z. Su, M.-S. Chen, J. Fan, M. Chen, S.-S. Chen, L. Luo, W.-Y. Sun. CrystEngComm, 12, 2040 (2010).
11] F.F.B.J. Janssen, L.P.J. Veraart, J.M.M. Smits, R. Gelder, A.E. Rowan. Cryst. Growth Des., 11, 4313
(
2011).
12] G.J. Halder, K.W. Chapman, S.M. Neville, B. Moubaraki, K.S. Murray, J.-F. Le
J. Am. Chem. Soc., 130, 17552 (2008).
13] A.J. Fletcher, E.J. Cussen, D. Bradshaw, M.J. Rosseinsky, K.M. Thomas. J. Am. Chem. Soc., 126, 9750
2004).
14] (a) S. Xiang, J. Huang, L. Li, J. Zhang, L. Jiang, X. Kuang, C.-Y. Su. Inorg. Chem., 50, 1743 (2011);
b) J. Jia, H.S. Athwal, A.J. Blake, N.R. Champness, P. Hubberstey, M. Schroder. Dalton Trans.,
0, 12342 (2011); (c) H. Li, W. Shi, K. Zhao, Z. Niu, X. Chen, P. Cheng. Chem. Eur. J., 18, 5715 (2012);
d) J. Huang, H. Li, J. Zhang, L. Jiang, C.-Y. Su. Inorg. Chim. Acta, 388, 16 (2012); (e) S.-J. Liu, L. Xue,
[
[
[
´
tard, C.J. Kepert.
(
(
4
(
¨
T.-L. Hu, X.-H. Bu. Dalton Trans., 41, 6813 (2012); (f) Q. Zhang, F. Hu, S. Wang, D. Sun, D. Wang,
J. Dou. Aust. J. Chem., 65, 524 (2012); (g) Y. Liu, H. Li, Y. Han, X. Lv, H. Hou, Y. Fan. Cryst. Growth
Des., 12, 3505 (2012).
[
15] (a) G.M. Sheldrick. SHELXS97, Program for Crystal Structure Solution, University of Go
Gottingen, Germany (1997); (b) G.M. Sheldrick. SHELXL97, Program for Crystal Structure Refinement,
University of Gottingen, Gottingen, Germany (1997).
¨
ttingen,
¨
¨
¨
[
16] (a) A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. Burla, G. Polidori, M. Camalli. J.
Appl. Cryst., 27, 435 (1994); (b) P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, R. de Gelder,
R. Israel, J.M.M. Smits. The DIRFID-99 program system, Technical Report of the Crystallography
Laboratory, University of Nijmegen, Nijmegen, The Netherlands (1999).

4
418
C. Hou et al.
[
17] Rigaku and Rigaku Americas. CrystalStructure 3.8: Crystal Structure Analysis Package, Rigaku and
Rigaku Americas, The Woodlands, TX (2000–2007).
[
[
18] A.T. Balaban. From Chemical Topology to Three-dimensional Geometry, Plenum Press, New York (1997).
19] (a) V.A. Blatov. IUCr CompComm Newsletter, 7, 4 (2006); (b) V.A. Blatov. TOPOS, A Multipurpose
Crystallochemical Analysis with the Program Package, Samara State University, Samara, Russia (2009).
20] (a) D. Tian, Y.-H. Zhou, L. Guan, H. Zhang. J. Coord. Chem., 64, 565 (2011); (b) D. Tian, L. Guan,
Y.-H. Zhou, H. Zhang. J. Coord. Chem., 64, 893 (2011); (c) M.L. Liu, Y.-X. Wang, W. Shi, J.-Z. Cui.
J. Coord. Chem., 65, 1915 (2012).
[
[
[
21] Z. Su, G.-C. Lv, J. Fan, G.-X. Liu, W.-Y. Sun. Inorg. Chem. Commun., 15, 317 (2012).
22] S.-L. Zheng, J.-H. Yang, X.-L. Yu, X.-M. Chen, W.-T. Wong. Inorg. Chem., 43, 830 (2004).