Syntheses, characterization and crystal structure of d10 coordination architectures: From 1D to 3D complexes based on mixed ligands

Article abstract of DOI:10.1016/j.ica.2012.05.037

Three coordination polymers, namely, [Zn₂(ndd) ₂(2,2′-bpy)₂·2H₂O]_n (1) [Cd(ndd)(2,2′-bpy)]_n (2), and [Cd(ndd)(1,4-pyb)]_n (3), where H₂ndd = 2,2′-(naphthalene-1,5-diylbis(oxy))diacetic acid, 1,4-pyb = 1,4-bis(pyridin-4-ylmethoxy)benzene and 2,2′-bpy = 2,2′-bipyridine, have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, powder X-ray diffraction and thermogravimetric analysis. Compound 1 can be considered as a 1D chain, which is further linked through the strongly multiple π-π interactions into a 3D supramolecular structure. By changing the metal ions, compound 2 is the 2D square structure (10.96 × 15.20 A) with the 4⁴·6² topology. By changing the auxiliary ligand, compound 3 presents a new (4,5)-connected 3D network with the point symbol of (4²·6⁵·8³)₂· (6⁶). Furthermore, compounds 1-3 show good fluorescence properties in the solid state at room temperature.

Full text of DOI:10.1016/j.ica.2012.05.037

Inorganica Chimica Acta 392 (2012) 77–83
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Inorganica Chimica Acta
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Syntheses, characterization and crystal structure of d10 coordination
architectures: From 1D to 3D complexes based on mixed ligands
⇑
⇑
⇑
Lian-Jie Li, Xin-Long Wang , Kui-Zhan Shao, Zhong-Min Su , Qiang Fu
Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China
a r t i c l e i n f o
a b s t r a c t
Three coordination polymers, namely, [Zn2(ndd)2(2,20-bpy)2ꢀ2H2O]n (1) [Cd(ndd)(2,20-bpy)]n (2), and
[Cd(ndd)(1,4-pyb)]n (3), where H2ndd = 2,20-(naphthalene-1,5-diylbis(oxy))diacetic acid, 1,4-pyb = 1,4-
bis(pyridin-4-ylmethoxy)benzene and 2,20-bpy = 2,20-bipyridine, have been synthesized under
hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, powder X-ray
diffraction and thermogravimetric analysis. Compound 1 can be considered as a 1D chain, which is
Article history:
Received 29 March 2012
Received in revised form 28 May 2012
Accepted 31 May 2012
Available online 1 July 2012
further linked through the strongly multiple
p–p interactions into a 3D supramolecular structure. By
Keywords:
changing the metal ions, compound 2 is the 2D square structure (10.96 ꢁ 15.20 Å) with the 44ꢀ62
topology. By changing the auxiliary ligand, compound 3 presents a new (4,5)-connected 3D network with
the point symbol of (42ꢀ65ꢀ83)2ꢀ(66). Furthermore, compounds 1–3 show good fluorescence properties in
the solid state at room temperature.
Coordination polymer
Hydrothermal synthesis
Crystal structure
Luminescent property
Crown Copyright Ó 2012 Published by Elsevier B.V. All rights reserved.
1. Introduction
transition-metal ions owing to the presence of –O–CH2– group
between the phenyl ring and carboxyl moiety; (ii) multidentate
The rational design and synthesis of coordination polymers has
undergone tremendous development owing to their potential
applications as functional materials, which include magnetism,
catalysis, luminescence, and gas sorption as well as their structural
diversities and intriguing topologies [1]. In recent years, a number
of coordination polymers with various structural types and
topological features have been documented [2]. The final struc-
tures of complexes can be effectively influenced by multiple factors
such as the coordination trend of metal centers, ligands, solvent
systems, templates, counteranions, temperature, pH values and
so on [3]. Among them, the most important ones are the geometri-
cal and electronic properties of the metal ions and ligands [4].
Thus, the judicious selection of metal ions and organic ligands play
an extremely important part in constructing novel 3D-
coordination network [5]. To date, a large number of metal carbox-
ylate coordination complexes have been reported [6]. In order to
assemble these molecular structures, carboxylate ligands are
frequently employed as bridging ligands to construct coordination
polymers [7]. Meanwhile, a fairly effective way to construct desir-
able networks is the introduction of multidentate flexible N-donor
ligands [8]. Thus, We explore the H2ndd ligand (2,20-(naphthalene-
1,5-diylbis(oxy))diacetic acid) to form coordination networks for
the following reasons: (i) it’s flexibility and conformational free-
dom allow them to meet the coordination environment of the
carboxylate ligands have proven to be good candidates for building
3D-coordination networks because of their diverse coordination
modes as well.
On the other hand, the d10 metal (CuI, AgI, AuI, ZnII, and CdII) com-
plexes have attracted considerable attention not only because they
exhibit appealing structures but also due to their good lumines-
cence properties [9]. As an interesting search for the coordination
networks, we adopt hydrothermal technique and successfully syn-
thesize three coordination polymers from 1D to 3D by changing
the metal ions and the auxiliary ligands. Accordingly, our aim is to
design and control the structure of crystals by using the different
types of metal ions and organic ligands. Herein, we have synthe-
sized the one-dimensional chain [Zn2(ndd)2(2,20-bpy)2ꢀ2H2O]n (1).
By translating the metal ions (CdII), we have obtained a two-dimen-
sional layer [Cd(ndd)(2,20-bpy)]n (2). By changing the auxiliary
ligands, we have acquired a 3D structure [Cd(ndd)(1,4-pyb)]n (3).
2. Experiment
2.1. Materials and physical methods
All reagents and solvents employed were commercially avail-
able and used as received without further purification. The ligands
H2ndd and 1,4-pyb were synthesized readily by the procedure re-
ported in the literature [10]. Elemental analyses (C, H, and N) were
performed on a Perkin-Elmer 240C elemental analyzer. The Fourier
transform infrared (FT-IR) spectra were recorded from KBr pellets
⇑
Corresponding authors.
E-mail address: zmsu@nenu.edu.cn (Z.-M. Su).
0020-1693/$ - see front matter Crown Copyright Ó 2012 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2012.05.037

78
L.-J. Li et al. / Inorganica Chimica Acta 392 (2012) 77–83
in the range 4000–500 cmꢂ1 on a Mattson Alpha-Centauri spec-
trometer (Figs. S1–S3). Solid-state luminescent spectra were mea-
sured on a Cary Eclipse spectrofluorometer (Varian) equipped with
a xenon lamp and quartz carrier at room temperature. Thermo-
gravimetric analysis (TGA) was performed on a Perkin-Elmer
TG-7 analyzer heated from 40 to 1000 °C under nitrogen.
928.76(m), 801.07(w), 779.47(w), 761.67(w), 734.59(w),
713.98(w), 648.09(m), 626.10(w), 586.77(m), 409.99(m).
2.4. Synthesis of [Cd)(ndd)(1,4-pyb)]n (3)
Compound 3 was synthesized in an analogous manner to com-
pound 2 except that 2,20-bpy was replaced by 1,4-pyb (0.2 mmol,
0.058 g). Colorless crystals of 3 were collected and washed with
distilled water and dried in air to give the product; yield, 47.5%
(based on CdII salts). Elemental Anal. Calc. for C32H26N2O8Cd
(678.97): C, 56.60; H, 3.85; N, 4.13. Found: C, 56.24; H, 3.30; N,
3.94%. IR (KBr pellet, cmꢂ1): 3424.20(m), 3079.12(m),
2927.57(m), 1746.93(s), 1620.62(w), 1594.19(w), 1507.74(w),
1411.21(w), 1327.18(w), 1268.91(w), 1246.48(w), 1229.55(w),
1171.30(m), 1097.52(m), 1055.41(m), 1019.32(m), 916.00(m),
875.72(m), 814.34(m), 778.81(m), 731.54(m), 626.65(m),
596.19(m), 485.23(m). The simulated and experimental PXRD
patterns of 1–3 are shown in Figs. S4–S6 (in the Supporting infor-
mation). The simulated and experimental PXRD patterns are in
good agreement with each other, indicating the phase purities of
the products. The differences in intensity may be due to the
preferred orientation of the powder samples.
2.2. Synthesis of [Zn2(ndd)2(2,20-bpy)2ꢀ2H2O]n (1)
A
mixture of Zn(Ac)2ꢀ2H2O (0.2 mmol, 0.044 g), H2ndd
(0.2 mmol, 0.055 g), 2,20-bpy (0.2 mmol, 0.031 g) in H2O (14 mL)
was sealed in a 25 mL Teflon-lined stainless steel container, which
was heated at 150 °C for 72 h and then cooled down to room tem-
perature at a rate of 5 °C hꢂ1. Colorless crystals of 1 were collected
and washed with distilled water and dried in air to give the prod-
uct; yield, 52.4% (based on ZnII salts). Elemental Anal. Calc. for
C
48H38N4O14Zn2 (1025.65): C, 56.21; H, 3.73; N, 5.46. Found: C,
55.35; H, 3.74; N, 4.83%. IR (KBr pellet, cmꢂ1): 3837.44(s),
3732.52(s), 3673.38(s), 3649.04(s), 3613.52(s), 3080.38(m),
1745.99(s), 1591.26(w), 1505.77(m), 1473.72(m), 1442.68(m),
1407.71(w), 1334.67(m), 1318.19(m), 1268.97(w), 1247.17(m),
1212.23(s), 1172.36(s), 1097.79(m), 1071.86(m), 1023.43(m),
973.67(m), 913.32(m), 874.16(s), 768.44(w), 718.58(m),
680.38(m), 632.41(m), 594.49(s), 412.90(s).
2.5. X-ray crystallography study
Data collection of complexes 1–3 were performed on a Bruker
Smart Apex II CCD diffractometer with graphite monochromated
2.3. Synthesis of [Cd(ndd)(2,20-bpy)]n (2)
Mo Ka radiation (k = 0.71073 Å) at room temperature. All absorp-
tion corrections were performed by using the SADABS program. The
Compound 2 was synthesized in an analogous manner to com-
pound 1 except that Zn(Ac)2ꢀ2H2O was replaced by Cd(Ac)2ꢀ2H2O
(0.2 mmol, 0.053 g). Colorless crystals of 2 were collected and
washed with distilled water and dried in air to give the product;
yield, 47.7% (based on CdII salts). Elemental Anal. Calc. for
Table 2
Selected bond lengths (Å) and angles (°) for complexes 1–3.
C
24H18N2O6Cd (542.82): C, 53.10; H, 3.34; N, 5.16. Found: C,
Complex 1
Zn(2)–N(1)
Zn(1)–N(3)
Zn(1)–O(1))A
Zn(2)–O(1W)
Zn(2)–O(4)
53.35; H, 2.84; N, 4.83%. IR (KBr pellet, cmꢂ1): 3444.41(s),
3057.13(s), 2911.58(s), 1597.87(w), 1573.91(w), 1506.08(w),
1478.92(m), 1409.55(w), 1347.09(w), 1326.43(w), 1274.81(w),
1247.21(w), 1209.28(w), 1168.87(w), 1097.05(w), 1015.13(w),
2.110(4)
2.125(4)
2.156(3)
2.116(3)
2.314(3)
2.057(3)
92.10(11)
94.59(12)
169.56(13)
149.01(14)
149.01(14)
155.68(11)
91.35(13)
59.31(12)
Zn(2)–N(2)
Zn(1)–N(4)
Zn(1)–O(2)A
Zn(1)–O(2W)
Zn(2)–O(5)
Zn(1)–O(11)
O(11)–Zn(1)–N(4)
O(11)–Zn(1)–N(3)
N(4)–Zn(1)–N(3)
O(2W)–Zn(1)–O(1)A
N(3)–Zn(1)–O(1)A
O(2W)–Zn(1)–O(2)A
N(3)–Zn(1)–O(2)A
2.112(4)
2.121(4)
2.278(3)
2.093(3)
2.125(3)
2.065(3)
111.65(13)
86.58(12)
76.31(15)
96.94(12)
93.51(13)
93.80(12)
91.57(13)
Zn(2)–O(8)
O(11)–Zn(1)–O(2W)
O(2W)–Zn(1)–N(4)
O(2W)–Zn(1)–N(3)
O(11)–Zn(1)–O(1)A
N(4)–Zn(1)–O(1)A
O(11)–Zn(1)–O(2)A
N(4)–Zn(1)–O(2)A
O(1)A–Zn(1)–O(2)A
Table 1
Crystal data and structure refinements for 1–3.
Complex
1
2
3
Formula
C
48H38N4O14Zn2 C24H18N2O6Cd C32H26N2O8Cd
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
1025.55
orthorhombic
Pna2(1)
14.207
23.962
12.772
90
90
90
4348
4
542.81
triclinic
Pbar1
678.96
monoclinic
P2(1)/c
19.780
18.275
7.890
90
101.197
90
2798
4
1.612
0.838
Complex 2
Cd(1)–O(1)
Cd(1)–N(1)
Cd(1)–O(4)
O(1)–Cd(1)–N(1)
O(1)–Cd(1)–O(3)
N(1)–Cd(1)–O(3)
N(2)–Cd(1)–O(4)
O(3)–Cd(1)–O(4)
10.471
10.911
10.963
63.106
80.411
82.789
1099.7
2
1.639
1.037
544.0
6714/4877
2.171(3)
Cd(1)–N(2)
2.324(3)
2.342(3)
Cd(1)–O(3)
2.416(3)
2.467(3)
O(1)–Cd(1)–N(2)
N(2)–Cd(1)–N(1)
N(2)–Cd(1)–O(3)
O(1)–Cd(1)–O(4)
N(1)–Cd(1)–O(4)
139.02(13)
71.00(12)
108.50(11)
134.49(12)
83.45(11)
a
(°)
105.96(14)
101.07(13)
135.96(11)
86.42(11)
53.10(9)
b (°)
c
(°)
V (Å3)
Z
Dcalc (g cmꢂ3
)
1.564
1.180
2096.0
21238/7593
l
(mmꢂ1
)
Complex 3
Cd(1)–O(7)
Cd(1)–N(1)
Cd(1)–O(1)B
O(7)–Cd(1)–N(2)A
N(2)A–Cd(1)–N(1)
N(2)A–Cd(1)–O(1)
O(7)–Cd(1)–O(1)B
N(1)–Cd(1)–O(1)B
O(7)–Cd(1)–O(2)B
N(1)–Cd(1)–O(2)B
O(1)B–Cd(1)–O(2)B
F(000)
Observed reflection/
unique
1376.0
16975/6583
2.230(4)
Cd(1)–N(2)A
2.307(4)
2.311(4)
Cd(1)–O(1)
2.374(4)
2.447(4)
Cd(1)–O(2)B
2.476(4)
Rint
0.0486
0.994
0.0204
1.003
0.0611
1.011
102.48(14)
170.20(16)
90.99(14)
111.25(15)
92.66(13)
163.51(15)
91.27(13)
53.10(12)
O(7)–Cd(1)–N(1)
O(7)–Cd(1)–O(1)
N(1)–Cd(1)–O(1)
N(2)A–Cd(1)–O(1)B
O(1)–Cd(1)–O(1)B
N(2)A–Cd(1)–O(2)B
O(1)–Cd(1)–O(2)B
83.85(14)
116.73(15)
79.42(14)
91.98(13)
129.96(8)
84.62(13)
77.54(12)
Goodness-of-fit (GOF)
on F2
R1a, wR2 [I > 2
r
(I)]
0.0360, 0.0701
0.0560, 0.0766
0.42
0.0386,
0.1023
0.0521,
0.1133
0.0454,
0.0862
0.1178,
0.1283
b
R1, wR2 (all data)
Flack parameter
a
R1
wR2 = |
=
R
||Fo| ꢂ |Fc||/
R|Fo|.
Symmetry codes: A, 1 + x, y, z for 1; A, 2 ꢂ x, ꢂy, ꢂ1 – z for 2; A, ꢂ1 + x, y, ꢂ1 + z; B, x,
0.5 ꢂ y, ꢂ0.5 + z for 3.
b
R
w(|Fo|2 ꢂ |Fc|2)|/
R .
|w(Fo2)2|1/2

L.-J. Li et al. / Inorganica Chimica Acta 392 (2012) 77–83
79
crystal structure was solved by direct methods and refined with
full-matrix least-squares (SHELXTL-97) [11] with atomic coordinates
and anisotropic thermal parameters for all nonhydrogen atoms.
The hydrogen atoms of aromatic rings were included in the
structure factor calculation at idealized positions by using a riding
model. In compound 1, H atoms of water molecules could not be
introduced in the refinement but were included in the structure
factor calculation. The detailed crystallographic data and structure
refinement parameters are summarized in Table 1. Selected bond
lengths and angles for complexes 1–3 are given in Table 2. Further
details of the crystal structure determination have been deposited
to the Cambridge Crystallographic Data center as Supplementary
publication.
adjacent chains possess weak
p
–
p
interactions, occur between
the adjacent 2,20-bpy ligands (parallel stacking with distances
centroid–centroid of 3.498 and 3.503 Å). The ring normal and the
vector between the ring centroids form an angle of about 0.5°, as
shown in Fig. 1b. Meanwhile, the
p–p stacking makes the whole
structure more stable (Fig. 1c). Remarkably, compound 1 crystal-
lizes in the non-centrosymmetric polar space group Pna21 [13].
Accordingly; the molecules must all be oriented in the same direc-
tion along the polar [001] directions. This polar packing within the
chain and of adjacent chains in the crystal of 1 probably originates
from the inter-chain p–p interactions [14]. The adjacent chains are
further connected through strongly multiple
form a layer.
p–p interactions to
3. Results and discussion
3.1.2. Structure of [Cd(ndd)(2,20-bpy)]n (2)
Compound 2 was obtained by changing the metal ions and it
shows
2D square structure with dimension of 10.963 ꢁ
3.1. Description of the crystal structures of 1–3
a
15.202 Å (the distance of adjacent dinuclear units) that is built
from dinuclear Cd2 units. The crystal structure of 2 contains one
CdII atom, one ndd ligand and one 2,20-bpy ligand in the asymmet-
ric unit. Each CdII ion is coordinated by four carboxylate oxygen
atoms (Cd–O 2.172(3)–2.416(3) Å) of two ndd ligands and two
nitrogen atoms (Cd–N 2.324(3)–2.342(3) Å) of one 2,20-bpy ligand
to complete the distorted octahedral coordination geometry. As
shown in Fig. 2a, the Cd–O and Cd–N bond distances are all in
the normal ranges [15]. Two crystallographically equivalent CdII
3.1.1. Structure of [Zn2(ndd)2(2,20-bpy)2ꢀ2H2O]n (1)
The single-crystal X-ray structural analysis reveals that com-
pound 1 crystallizes in the orthorhombic space group Pna21 and
the asymmetric unit of 1 consists of two ZnII ions, two ndd ligands,
two 2,20-bpy ligands and two lattice water molecules. Each ZnII ion
is coordinated by three carboxylate oxygen atoms of two ndd
ligands, one oxygen atom of one water molecule and two nitrogen
atoms of one 2,20-bpy ligand to furnish the distorted octahedral
coordination geometry, as shown in Fig. 1a. The Zn–O (2.057(3)–
2.314(3) Å) and Zn–N (2.110(4)–2.125(4) Å) bond distances are
all in the normal ranges [12].
atoms are bridged by two l2-carboxylates oxygen giving a shaped
SBU [Cd2(CO2)4N2] in which the Cdꢀ ꢀ ꢀCd distance is 3.9446(12) Å.
In compound 2, the ndd ligand can be considered as a linear lin-
ker. All Cd atoms are connected by carboxyl groups and pyridyl-N
atoms of 2,20-bpy ligands, thus forming novel shape of framework
{Cd4O36C42N8}, as illustrated in Fig. 2b. Meanwhile, each dinuclear
units can be considered as a node, each node is attached to four
ndd ligands and two 2,20-bpy ligands, which can be considered as
The structure of compound 1 is an infinite zigzag chain con-
structed by zinc ions and ndd ligands, decorated with bidentate
2,20-bpy ligands. The ndd ligand coordinates to metal in a bis-
monodentate and bis-bidentate fashion to generate one-
dimensional chain (Fig. S7 in the Supporting information). The
Fig. 1. (a) Coordination environment of ZnII in 1 with the ellipsoids drawn at the 30% probability level and hydrogen atoms were omitted for clarity (symmetry
transformations used to generate equivalent atoms: A, 1 + x, y, z). (b) The compound 1 is packed by the
p–p interactions along the axis. (c) Schematic view of the 3D
supramolecular structure.

80
L.-J. Li et al. / Inorganica Chimica Acta 392 (2012) 77–83
Fig. 2. (a) Coordination environment of CdII atom in 1 with the ellipsoids drawn at the 30% probability level and hydrogen atoms were omitted for clarity (symmetry
transformations used to generate equivalent atoms: A, 2 ꢂ x, ꢂy, 1 ꢂ z). (b) Ball-and-stick and schematic representation of the (4,4) nets in the structure of 2. (c) Schematic
view of the 4-connected net of 2 with (44ꢀ62) topology. (d) The packing mode of 2D nets in 2.
Fig. 3. (a) View of the 1D chain. (b and c) View of the 2D layer structure of compound 3. (d) Schematic representation of the 3D-coordination network.
a 4-connected node; While, each ndd ligand can be seen as a linear
linker between two nodes. Thus, a distorted 2D network sustained
by 4-connected nodes is then yielded, as illustrated in Fig. 2c. The
2D nets are packing in –aaa– mode as show in Fig. 2d. Each win-
dow shows dimension of 10.963 ꢁ 15.202 Å2 for each side: Each
window shows dimension of 10.963 ꢁ 15.202 Å2 for each side:
centroid distances of 3.791 Å [16]. Significant
p
–
p
and C–Hꢀ ꢀ ꢀ
p
(edge-to-face separation 3.428 and 3.576 Å) supramolecular inter-
actions between the aromatic rings contained in this structure sta-
bilize the structure adopted.
3.1.3. Structure of [Cd(ndd)(1,4-pyb)]n (3)
p–p
stacking interactions exist between pyridine and aromatic
Compound 3, obtained by changing the auxiliary ligands, is a
3D-coordination network. The single-crystal X-ray structural anal-
ysis reveals that compound 3 crystallizes in the monoclinic space
rings from adjacent layers. The ring normal and the vector between
the ring centroids form an angle of about 8.431° up to centroid–

L.-J. Li et al. / Inorganica Chimica Acta 392 (2012) 77–83
81
Fig. 4. Ball-and-stick and polyhedral representations of the 1,4-pyb line linker, 4-connected ndd ligand and 5-connected mononuclear cadmium.
group P2(1)/c and the asymmetric unit of 3 consists of one CdII ion,
one ndd ligand and one 1,4-pyb ligand. Each CdII ion is coordinated
by four oxygen atoms from three ndd ligands and two N sites from
two 1,4-pyb ligands to furnish the distorted octahedral coordina-
tion geometry, as shown in Fig. S8 (in the Supporting information).
The Cd–O (2.230(4)–2.476(4) Å) and Cd–N (2.307(4)–2.311(4) Å)
bond distances are all in the normal ranges [15]. In compound 3,
the two carboxlate groups of H2ndd exhibit the two types of coor-
dination modes, one is bis(monodentate) coordination mode and
the other is tridentate coordination mode (Fig. S9 in the Supporting
information). Apart from the bis(monodentate), such a tridentate
bridge mode is a key factor for the formation of the multinuclear
cluster.
In order to interpret the whole network clearly, the structure of
3 could be described as –Cd–O–Cd– chain (Fig. 3a), which is
constructed by bridging
l2-carboxylate oxygens and Cd ions. In
Fig. 5. Schematic representation of the (4,5)-connected network with point symbol
of (42ꢀ65ꢀ83)2ꢀ(66).
addition, the adjacent chains were connected to built a 2D layer
structure with the Cdꢀ ꢀ ꢀCd distance of 4.362 Å. In the network,
there are the two types of building blocks (Fig. 3b and c): one is
formed to shape of framework [Cd5O36C34] (Fig. S10 in the Support-
ing information), which is constructed by the ndd ligands and CdII
ions; the other is constructed to shape of framework [Cd4O18C36N8]
(Fig. S11 in the Supporting information), which is constructed by
the 1,4-pyb ligands and CdII ions. Finally, the adjacent layers were
linked by the ndd ligands to lead to a complicated 3D network
(Fig. 3d).
[19]. As far as we know, the only one example of the 3D-coordina-
tion network is the complex [Cd2(btec)(btb)3](H2O)10(btb =
1,4-bis(1,2,4-triazol-1-yl)butane, btec = 1,2,4,5-benzenetetracarb-
oxylate) [20]. The different of this compound is that compound 3
exhibits –Cd–O–Cd– chain.
3.2. The thermal and photoluminescent properties of 1–3
The construction of the topological network and the topolog-
ical analysis of the structure were performed using OLEX along
with TOPOS program [17]. The mononuclear cadmium is treated
as a single node. The ndd ligand is considered as the 4-connected
node owing to the ndd ligand connects four cadmium atoms.
Meanwhile, each 1,4-pyb ligand is considered as the line linker
and each cadmium atom is considered as a 5-connected node
(Fig. 4), the overall structure of complex 3 is an extended neutral
3D (4,5)-connected network with the point symbol of
(42ꢀ65ꢀ83)2ꢀ(66) (Fig. 5).
The photoluminescent properties of 1–3 and the free ligand
H2ndd were examined in the solid state at room temperature. As
shown in Fig. 6, the main emission peak of H2ndd is at 474 nm
(kex = 363 nm). Compound
1 shows the emission maxima at
457 nm (kex = 388 nm). While, compound 2 shows the emission
maxima at 498 nm (kex = 336 nm). Compound 3 shows the emis-
sion maxima at 450 nm (kex = 370 nm). In comparison with that
of the free ligand, the maximum emission wavelengths of com-
pounds 1 and 3 exhibit slight blue-shift, which is probably due
to intraligand charge transitions, On the contrary, compound 2
shows slight red-shift, which might be attributed to intraligand
charge transitions [21].
According to present literature, the one known example of a
(1D ? 3D) chain is the compound [[Zn(L)(phen)(H2O)]n (L = 2,20-
(naphthalene-1,5-diylbis(oxy))diacetic acid, Phen = 1,10-phenan-
throline] reported by us very recently [18]. Differing from the
compound 1 is auxiliary ligands (2,20-bpy is changed to Phen). A
few crystal structures have been observed for the compound 2
The TGA of compounds 1–3 have been investigated in order to
characterize the three compounds more fully in terms of their ther-
mal stability, as shown in Fig. 7. For compound 1, the weight loss

82
L.-J. Li et al. / Inorganica Chimica Acta 392 (2012) 77–83
Acknowledgments
The authors gratefully acknowledge the financial support from
the NNSF of China (No. 21001022, 21171033, 21131001), The
NGFR 973 Program of China (2010CB635114), NCET in Chinese
University (NCET-10-0282), PhD Station Foundation of Ministry
of Education (20100043110003), The FANEDD of PR China (No.
201022), The STDP of Jilin Province (201001169, 20111803), The
FRFCU (09ZDQD003, 10CXTD001) and The Fundamental Research
Funds for the Central Universities (11SSXT130).
Appendix A. Supplementary material
CCDC 860060–860062 contain the supplementary crystallo-
graphic data for compounds 1–3. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at http://
dx.doi.org/10.1016/j.ica.2012.05.037.
Fig. 6. Emission spectra of compounds 1–3 and H2ndd in the solid state at room
temperature.
References
[1] (a) C. Janiak, J.K. Vieth, New J. Chem. 34 (2010) 2366;
(b) U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre, J.
Mater. Chem. 16 (2006) 626;
(c) J. Larionova, Y. Guari, C. Sangregorio, C. Guérin, New J. Chem. 33 (2009)
1177;
(d) K. Drabent, Z. Ciunik, A. Ozarowski, Inorg. Chem. 47 (2008) 3358;
(e) S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita,
S. Kitagawa, J. Am. Chem. Soc. 129 (2007) 2607;
(f) M.D. Allendorf, C.A. Bauer, R.K. Bhakta, R.J.T. Houk, Chem. Soc. Rev. 38
(2009) 1330;
(g) S.L. Zheng, X.M. Chen, Aust. J. Chem. 57 (2004) 703;
(h) C. Gao, S. Liu, L. Xie, C. Sun, J. Cao, Y. Ren, D. Feng, Z. Su, CrystEngComm 11
(2009) 177;
(i) K. Li, J.Y. Lee, D.H. Olson, T.J. Emge, W. Bi, M.J. Eibling, J. Li, Chem. Commun.
(2008) 6123;
(j) L. Carlucci, G. Ciani, D.M. Proserpio, Coord. Chem. Rev. 246 (2003) 247;
(k) X.L. Wang, C. Qin, E.B. Wang, Y.G. Li, Z.M. Su, L. Xu, L. Carlucci, Angew.
Chem., Int. Ed. 44 (2005) 5824.
[2] (a) P. Jensen, D.J. Price, S.R. Batten, B. Moubaraki, K.S. Murray, Chem. Eur. J. 6
(2000) 3186;
Fig. 7. The TGA curves of 1–3.
(b) S.H. Chiu, S.J. Rowan, S.J. Cantrill, J.F. Stoddart, A.J.P. White, D.J. Williams,
Chem. Commun. (2002) 2948;
(c) B. Moulton, H. Abourahma, M.W. Bradner, J.J. Lu, G.J. McManus, M.J.
Zaworotko, Chem. Commun. (2003) 1342;
corresponding to the release of a lattice water molecule is observed
(obsd 3.51%, calcd 4.08%). The dehydrated complex is stable up to
319 °C. The frameworks collapsed in the temperature range of
319–823 °C. The remaining weight corresponds to the formation
of ZnO (obsd 10.37%, calcd 15.80%). The TGA study of compound
2 shows no weight loss from room temperature to 336 °C, suggest-
ing that the frameworks are thermally stable. Above 336 °C, a rapid
weight loss is observed which is attributed to the burning of the or-
ganic ligands. The TGA study of compound 3 shows no weight loss
from room temperature to 330 °C. Above 330 °C, a rapid weight
loss is observed which is attributed to the burning of the organic
ligands.
(d) R. Vaidhyanathan, S. Natarajan, C.N.R. Rao, Cryst. Growth Des. 3 (2003) 47;
(e) T.J. Prior, M.J. Rosseinsky, Inorg. Chem. 42 (2003) 1564;
(f) S.R. Batten, R. Robson, Angew. Chem., Int. Ed. 37 (1998) 1460.
[3] (a) S. Noro, S. Kitagawa, M. Kondo, K. Seki, Angew. Chem., Int. Ed. 39 (2000)
2081;
(b) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629;
M. Eddaoudi, J. Kim, N.L. Rosi, D.T. Vodak, J. Wachter, M. O’Keeffe, O.M. Yaghi,
Science 295 (2002) 469;
(d) L. Pan, M.B. Sander, X.Y. Huang, J. Li, M. Smith, E. Bittner, B. Bochrath, J.K.
Johnson, J. Am. Chem. Soc. 126 (2004) 1308;
(e) K. Biradha, M. Sarkar, L. Rajput, Chem. Commun. (2006) 4169.
[4] (a) L. Beitone, C. Huguenard, A. Gansmuller, M. Henry, F. Taulelle, T. Loiseau, G.
Férey, J. Am. Chem. Soc. 125 (2003) 9102;
(b) H.W. Roesky, M. Andruh, Coord. Chem. Rev. 236 (2003) 91;
(c) S.A. Barnett, N.R. Champness, Coord. Chem. Rev. 246 (2003) 145;
(d) L. Pan, D.H. Olson, L.R. Ciemnolonski, R. Heddy, J. Li, Angew. Chem., Int. Ed.
45 (2006) 616.
4. Conclusions
[5] (a) X.L. Wang, C. Qin, E.B. Wang, L. Xu, Z.M. Su, C.W. Hu, Angew. Chem., Int. Ed.
43 (2004) 5036;
(b) Z.H. Zhang, T.A. Okamura, Y. Hasegawa, H. Kawaguchi, L.Y. Kong, W.Y. Sun,
N. Ueyama, Inorg. Chem. 44 (2005) 6219;
(c) M. Oh, G.B. Carpenter, D.A. Sweigart, Acc. Chem. Res. 37 (2004) 1;
(d) Q.R. Fang, G.S. Zhu, Z. Jin, M. Xue, X. Wei, D.J. Wang, S.L. Qiu, Angew. Chem.,
Int. Ed. 45 (2006) 6126.
In summary, we have synthesized and characterized three new
coordination polymers by using 2,20-(naphthalene-1,5-diyl-
bis(oxy))diacetic acid, 2,20-bipyridine and 1,4-bis(pyridin-4-
ylmethoxy)benzene ligands. Compound 1 is a 1D chain, which is
[6] (a) C. Janiak, Dalton Trans. (2003) 2781;
constructed to a 3D supramolecule structure by the strong
p–p
(b) S.R. Batten, CrystEngComm 18 (2001) 1;
interactions. By changing the metal ions, we have obtained a 2D
layer with the 44ꢀ62 topology. Meanwhile, by changing the auxil-
iary ligands, we have acquired a 3D-coordination network. More-
over, compounds 1–3 show good fluorescence properties in the
solid state at room temperature.
(c) N.W. Ockwig, O. Delgado-Friedrichs, M. O’Keeffe, O.M. Yaghi, Acc. Chem.
Res. 38 (2005) 176;
(d) C.N.R. Rao, S. Natarajan, R. Vaidhyanathan, Angew. Chem., Int. Ed. 43 (2004)
1466;
(e) V.A. Blatov, L. Carlucci, G. Ciani, D.M. Proserpio, CrystEngComm 6 (2004)
377.

L.-J. Li et al. / Inorganica Chimica Acta 392 (2012) 77–83
83
[7] (a) H.A. Habib, J. Sanchiz, C. Janiak, Dalton Trans. (2008) 1734;
(b) C.B. Aakeröy, N.R. Champness, C. Janiak, Dalton Trans. (2009) 1742;
(c) H.A. Habib, J. Sanchiz, C. Janiak, Inorg. Chim. Acta 362 (2009) 2452.
[8] (a) B. Wisser, Y. Lu, C. Janiak, Z. Anorg. Allg. Chem. 633 (2007) 1189;
(b) S.K. Henninger, H.A. Habib, C. Janiak, J. Am. Chem. Soc. 131 (2009) 2776;
(c) C.B. Aakeröy, N.R. Champness, C. Janiak, CrystEngComm 12 (2010) 22.
[9] (a) S.L. Zheng, J.H. Yang, X.L. Yu, X.M. Chen, W.T. Wong, Inorg. Chem. 43 (2004)
830;
(c) A.C. Chamayou, M.A. Neelakantan, S. Thalamuthu, C. Janiak, Inorg. Chim.
Acta. 365 (2011) 447.
(d) M. Enamullah, A. Sharmin, M. Hasegawa, T. Hoshi, A.C. Chamayou, C. Janiak,
Eur. J. Inorg. Chem. (2006) 2146.
[15] (a) R.H. Wang, M.C. Hong, J.H. Luo, R. Cao, J.B. Weng, Chem. Commun. (2003)
1018;
(b) X.J. Luan, X.H. Cai, Y.Y. Wang, D.S. Li, C.J. Wang, P. Liu, H.M. Hu, Q.Z. Shi, S.M.
Peng, Chem. Eur. J. 12 (2006) 6281;
(b) M.C. Hong, Y.J. Zhao, W.P. Su, R. Cao, M. Fujita, Z.Y. Zhou, A.S.C. Chan,
Angew. Chem., Int. Ed. 39 (2000) 2468;
(c) E.C. Yang, H.K. Zhao, B. Ding, X.G. Wang, X.J. Zhao, Cryst. Growth Des. 7
(2007) 2009;
(c) F.A.A. Paz, J. Klinowski, Inorg. Chem. 43 (2004) 3948.
[16] C. Janiak, J. Chem. Soc., Dalton Trans. (2000) 3885.
[17] (a) O.V. Dolomanov, A.J. Blake, N.R. Champness, M. Schröder, J. Appl.
Crystallogr. 36 (2003) 1283;
(d) X.W. Wang, J.Z. Chen, J.H. Liu, Cryst. Growth Des. 7 (2007) 1227.
[10] (a) P. Mondal, A. Karmakar, W.M. Singh, J.B. Baruah, CryEngComm 10 (2008)
1550;
(b) V.A. Blatov, A.P. Shevchenko, V.N. Serezhkin, J. Appl. Crystallogr. 33 (2000)
1193;
(c) V.A. Blatov, A.P. Shevchenko, V.N. Serezhkin, Acta Crystallogr., Sect. A 51
(1995) 909;
(d) V.A. Blatov, A.P. Shevchenko, V.N. Serezhkin, J. Appl. Crystallogr. 32 (1999)
377.
(b) L.P. Zhang, C.K. Lam, H.B. Song, T.C.W. Mak, Polyhedron 23 (2004) 2413;
(c) H.W. Hou, T.Y. Fan, L.P. Zhang, C.X. Du, Y. Zhu, Inorg. Chem. Commun. 4
(2001) 168;
(d) L.J. Li, C. Qin, X.L. Wang, S. Wang, L. Zhao, G.S. Yang, H.N. Wang, G. Yuan,
K.Z. Shao, Z.M. Su, CrystEngComm 14 (2012) 124;
[18] L.J. Li, X.L. Wang, L. Zhao, K.Z. Shao, H.N. Wang, G. Yuan, Z.M. Su, Inorg. Chem.
Commun. 15 (2012) 288.
(e) L.J. Li, C. Qin, X.L. Wang, K.Z. Shao, Z.M. Su, P.J. Liu. CryEngComm. 14 (2012)
4205.
[11] G.M. Sheldrick, SHELXL-97, Program for X-ray Crystal Structure Refinement,
University of Göttingen, Göttingen, Germany, 1997.
[12] (a) X.M. Zhang, M.L. Tong, M.L. Gong, X.M. Chen, Eur. J. Inorg. Chem. (2003)
138;
(b) A.D. Burrows, R.W. Harrington, M.F. Mahon, S.J. Teat, Eur. J. Inorg. Chem.
(2003) 766.
[13] (a) H.D. Flack, M. Sadki, A.L. Thompson, D.J. Watkin, Acta Crystallogr., Sect. A
67 (2011) 21;
[19] (a) G.B. Li, J.M. Liu, Y.P. Cai, C.Y. Su, Cryst. Growth Des. 11 (2011) 2939;
(b) Q. Yang, X.F. Zhang, J.P. Zhao, B.W. Hu, X.H. Bu, Cryst. Growth Des. 11
(2011) 2763.
[20] L.Y. Wang, Y. Yang, K. Liu, B.L. Li, Y. Zhang, Cryst. Growth Des. 8 (2008) 3902.
[21] (a) H.A. Habib, J. Sanchiz, C. Janiak, Dalton Trans. (2008) 1734;
(b) W.L. Liu, L.H. Ye, X.F. Liu, L.M. Yuan, J.X. Jiang, C.G. Yan, CrystEngComm 10
(2008) 1395;
(c) S.Q. Zang, Y. Su, Y.Z. Li, J.G. Lin, X.Y. Duan, Q.J. Meng, S. Gao, CrystEngComm
11 (2009) 122;
(d) P. Ren, M.L. Liu, J. Zhang, W. Shi, P. Cheng, D.Z. Liao, S.P. Yan, Dalton Trans.
(2008) 4711;
(e) H.A. Habib, A. Hoffmann, H.A. Höppea, C. Janiak, Dalton Trans. (2009) 1742;
(f) H.A. Habib, A. Hoffmann, H.A. Höppe, G. Steinfeld, C. Janiak, Inorg. Chem. 48
(2009) 2166;
(b) H.D. Flack, G. Bernardinelli, Chirality 20 (2008) 681;
(c) H.D. Flack, G. Bernardinelli, Acta Crystallogr., Sect. A 55 (1999) 908.
[14] (a) B. Gil-Hernández, H.A. Höppe, J.K. Vieth, J. Sanchiz, C. Janiak, Chem.
Commun. (2010) 8270;
(b) C. Janiak, A.C. Chamayou, A.K.M. Royhan Uddin, M. Uddin, K.S. Hagenc, M.
Enamullah, Dalton Trans. (2009) 3698;
(g) S.L. Zheng, X.M. Chen, Aust. J. Chem. 57 (2004) 703.