Syntheses and structural characterization of three coordination polymers of Cd(II), Zn(II) and Pb(II) with the "V" shape ligand 4,4′-[isopropylidenebis(p-phenyleneoxy)]diacetic acid

Article abstract of DOI:10.1016/j.molstruc.2009.11.018

Three new inorganic-organic coordination polymers based on a "V" shape linking unit 4,4′-[isopropylidenebis(p-phenyleneoxy)]diacetic acid (H₂L) and Cd^II, Zn^II and Pb^II ions, [Cd(L)(H₂O)₂]

Full text of DOI:10.1016/j.molstruc.2009.11.018

Journal of Molecular Structure 964 (2010) 109–118
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Syntheses and structural characterization of three coordination
polymers of Cd(II), Zn(II) and Pb(II) with the ‘‘V” shape ligand
4,40-[isopropylidenebis(p-phenyleneoxy)]diacetic acid
a
b
a
a
Ze-Bao Zheng a, , Ren-Tao Wu , Ji-Kun Li , Yi-Feng Sun , Yin-Feng Han
*
a Department of Chemistry and Environmental Science, Taishan University, Taian, Shandong 271021, PR China
b Department of Materials and Chemical Engineering, Taishan University, Taian, Shandong 271021, PR China
a r t i c l e i n f o
a b s t r a c t
Three new inorganic–organic coordination polymers based on a ‘‘V” shape linking unit 4,40-[isopropylid-
enebis(p-phenyleneoxy)]diacetic acid (H2L) and CdII, ZnII and PbII ions, [Cd(L)(H2O)2]n (1), [Zn2(L)3-
(H2O)6ꢀ6H2O]n (2) and [Pb2Na2(L)3(DMF)4(H2O)2ꢀ2H2O]n (3), have been prepared and structurally charac-
terized by single-crystal X-ray diffraction analysis. Complex 1 is a 1D zig-zag chain coordination polymer,
which is connected by strong hydrogen-bond interactions to result in a 3D network. In complex 2, an infi-
nite 2D (6, 3) network with large hexagonal cavities was created. The whole 2D structure is a noninter-
Article history:
Received 6 September 2009
Accepted 5 November 2009
Available online 11 November 2009
Keywords:
4,40-[Isopropylidenebis-
(p-phenyleneoxy)]diacetic acid
‘‘V” shape building block
Coordination polymers
Heterometallic
penetrating framework stacked by hydrogen-bonding interactions. Complex
3 is a novel 3D
heterometallic coordination polymer, which possesses three different types of isolated channels.
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
carboxylic acids have two or more carboxyl groups that can be
completely or partially deprotonated, which results in a rich vari-
Nowadays, the design and preparation of metal–organic frame-
works (MOFs) are still one of the most focused areas of research
[1–4]. The rational design and synthesis of such novel coordination
polymers are of great current interest in the field of supramolecu-
lar chemistry and crystal engineering [5–7], not only because of
their intriguing structural motifs, but also because of their poten-
tial for a variety of applications [8–10]. As far as we know, the for-
mation of MOFs is influenced by many factors, such as metal ions,
organic ligands, counterions, solvent molecules and pH of the reac-
tion mixture, etc. [11,12]. Among these factors, the selection of or-
ganic ligands is one of the most important aspects [13,14]. The
configuration, rigidity, substituent and coordination modes of or-
ganic ligands have an important effect on the final structures.
One of the most efficient routes to coordination polymers is to em-
ploy a multifunctional ligand to link metal ions into an infinite
framework. Flexible di- and polycarboxylic acids are good candi-
dates for the construction of novel metal–organic compounds as
the carboxyl groups can form CAOAMAO four-membered rings
with central metal ions, thereby improving the stability of transi-
tion metal–organic frameworks (MOFs). Furthermore, di- and poly-
ety of coordination modes and many interesting structures with
higher dimensions. In light of the above, more and more attention
has been paid to the use of flexible di- and polycarboxylate ligands
[15–17], whereas studies involving semi-rigid V-shaped dicarbox-
ylate ligands are relatively scarce [18–22]. 4,40-[Isopropylidene-
bis(p-phenyleneoxy)]diacetic acid is a typical example of semi-
rigid V-shaped dicarboxylate ligands. To the best of our knowledge,
there has been no report about its coordination compounds. Here-
in, we report the synthesis and structures of three novel coordina-
tion polymers of 4,40-[isopropylidenebis(p-phenyleneoxy)]diacetic
acid, namely [Cd(L)(H2O)2]n (1), [Zn2(L)3(H2O)6ꢀ6H2O]n (2) and
[Pb2Na2(L)3(DMF)4(H2O)2ꢀ2H2O]n (3).
2. Experimental
2.1. Materials and methods
The solvents and reagents for synthesis were commercially
available and used as received. The ligand 4,40-[isopropylidene-
bis(p-phenyleneoxy)]diacetic acid (H2L) was synthesized by the lit-
erature method [23]. Elemental analyses (C, H and N) were
performed on a Perkin-Elmer 240C analyzer and IR spectra were
measured on a Tensor 27 OPUS (Bruker) FT-IR spectrometer with
KBr pellets. Thermogravimetric analysis (TGA) were carried out
on a Delta Series TA-SDTQ600 in nitrogen atmosphere from room
* Corresponding author. Address: Department of Chemistry and Environmental
Science, Taishan University, Yingbin Street, Taian, Shandong 271021, PR China. Tel.:
+86 538 6715546; fax: +86 538 6715546.
E-mail address: zhengzebao@163.com (Z.-B. Zheng).
0022-2860/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2009.11.018

110
Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
Table 1
Table 2
Crystal, data collection and structure refinement parameters for complexes 1–3.
Selected bond lengths (Å) and angles (°) for complexes 1–3.
Complex
1
2
3
Compound 1
Cd(1)AO(4)
Cd(1)AO(3)
2.212(7)
2.444(7)
95.9(5)
141.9(3)
102.6(3)
82.6(4)
Cd(1)AO(2)
2.351(8)
Empirical
formula
Formula weight 490.77
Wavelength, (Å) 0.71073
Crystal system
Space group
a (Å)
C19H22CdO8
C57H78Zn2O30
C69H90Pb2Na2N4O26
O(4)ACd(1)AO(4)#1
O(4)ACd(1)AO(2)#1
O(4)ACd(1)AO(2)
O(2)#1ACd(1)AO(2)
O(4)ACd(1)AO(3)
O(2)#1ACd(1)AO(3)
O(2)ACd(1)AO(3)
O(4)#1ACd(1)AO(3)#1
O(4)#1ACd(1)AO(3)
O(3)ACd(1)AO(3)#1
87.5(3)
55.0(2)
126.6(3)
87.3(3)
131.5(3)
1373.93
0.71073
Trigonal
P-3c1
20.411(8)
20.411(8)
9.784(7)
90
1851.81
0.71073
Monoclinic
C2/c
39.364(3)
22.001(2)
8.846(7)
90
Orthorhombic
Ama2
28.130(6)
11.847(2)
5.588(1)
90
126.6(3)
Compound 2
Zn(1)AO(2)
O(2)AZn(1)AO(2)#2
O(2)AZn(1)AO(4)
O(2)#2AZn(1)AO(4)
b (Å)
c (Å)
2.117(4)
Zn(1)AO(4)
O(4)AZn(1)AO(4) #2
O(2)AZn(1)AO(4) #2
2.120(4)
88.37(14)
93.17(14)
88.90(13)
89.61(14)
177.42(14)
a
(°)
b (°)
90
90
90
120
96.888(3)
90
c
(°)
Z
4
2
4
Compound 3
Pb(1)AO(10)
Pb(1)AO(3)
Pb(1)AO(2)
Pb(1)AO(4)
Pb(1)AO(1)
Pb(1)AO(8)
Pb(1)AO(10) #3
Pb(1)AO(3) #3
O(10)APb(1)AO(3)
O(10)APb(1)AO(2)
O(3)APb(1)AO(2)
O(10)APb(1)AO(4)
O(3)APb(1)AO(4)
O(2)APb(1)AO(4)
O(1)ANa(1)AO(11)
O(1)ANa(1)AO(12)
O(11)ANa(1)AO(12)
O(1)ANa(1)AO(2)#3
O(11)ANa(1)AO(2)#3
Dcalc(Mg mꢁ3
F(000)
)
1.750
992
1.218
1.293
1440
0.759
1.617
3704
4.513
2.431(4)
2.439(4)
2.444(4)
2.762(4)
2.835(3)
2.850(4)
2.891(4)
3.075(2)
78.86(14)
84.56(13)
70.02(13)
116.11(13)
49.69(13)
105.39(13)
161.33(19)
73.41(15)
88.65(18)
87.31(15)
101.01(17)
Pb(1)AO(9)
Na(1)AO(1)
Na(1)AO(11)
Na(1)AO(12)
Na(1)AO(2)#3
Na(1)AO(3)#3
Na(1)AO9
3.158(2)
2.369(4)
2.374(5)
2.416(5)
2.434(4)
2.469(5)
2.479(4)
l
(mmꢁ1
)
Crystal size (mm) 0.28 ꢂ 0.20 ꢂ 0.15 0.15 ꢂ 0.13 ꢂ 0.11 0.30 ꢂ 0.18 ꢂ 0.08
h Range (°)
Index ranges
2.90–24.97
ꢁ33 6 h 6 32;
ꢁ14 6 k 6 13;
ꢁ6 6 l 6 6
10,128
2.00–25.05
ꢁ23 6 h 6 24;
ꢁ19 6 k 6 24;
ꢁ11 6 l 6 11
17,528
1.04–25.00
ꢁ46 6 h 6 46;
ꢁ26 6 k 6 26;
ꢁ9 6 l 6 10
43,026
Reflections
collected
Unique
reflections
Data/restraints/
parameters
Goodness of fit
on F2
O(12)ANa(1)AO(2)#3
O(1)ANa(1)AO(3)#3
O(11)ANa(1)AO(3)#3
O(12)ANa(1)AO(3)#3
O(2)#3ANa(1)AO(3)#3
O(1)ANa(1)AO9
O(11)ANa(1)AO9
O(12)ANa(1)AO9
O(2)#3ANa(1)AO9
O(3)#3ANa(1)AO9
99.42(18)
101.24(15)
97.34(18)
168.34(18)
69.68(13)
82.08(14)
98.67(17)
106.79(19)
147.41(15)
82.27(15)
1660
(Rint = 0.0557)
1660/0/135
2040
(Rint = 0.0883)
2040/0/136
6717
(Rint = 0.0677)
6717/0/494
1.194
1.009
1.113
Final R indices
[I > 2
R indices(all data) R1 = 0.0740,
R1 = 0.0706,
wR2 = 0.1597
R1 = 0.0699,
wR2 = 0.1858
R1 = 0.1194,
wR2 = 0.2255
0.616/ꢁ0.420
R1 = 0.0371,
wR2 = 0.0969
R1 = 0.0529,
wR2 = 0.1118
1.238/ꢁ1.197
r
(I)]
wR2 = 0.1614
Largest difference 2.309/ꢁ0.917
in peak and
Symmetry transformations used to generate equivalent atoms: #1 ꢁx + 1, ꢁy, z;
#2 ꢁy + 1, x ꢁ y, z; #3 x, ꢁy + 1, z ꢁ ½.
hole (e Åꢁ3
)
25 ml Teflon-lined stainless steel reactor, and then heated at
140 °C for 72 h, upon cooling to room temperature, colorless acic-
ular single crystals were collected and dried in air. Yield: 40%
(based on Cd). Anal. Calcd. for C19H22CdO8: C, 46.50; H, 4.52.
Found: C, 46.39; H, 4.43. IR (KBr, cmꢁ1): 3410(s), 2928(w),
2849(w), 1607(m), 1563(s), 1512(s), 1434(m), 1339(s), 1248(s),
1188(m), 1073(m), 835(m), 737(w), 570(w).
temperature to 1000 °C (heating rate = 10 °C minꢁ1) using alumin-
ium crucibles.
2.2. Syntheses
2.2.1. [Cd(L)(H2O)2]n (1)
A mixture of Cd(CH3COO)2ꢀ2H2O (0.135 g, 0.5 mmol) and H2L
(0.172 g, 0.5 mmol) were dissolved in water (12 ml) and ethanol
(3 ml), the pH of the solution was adjusted to be about 6–7 with
0.2 mol Lꢁ1 aqueous NaOH, then the mixed solution was stirred
for 30 min at room temperature, transferred to and sealed in a
2.2.2. [Zn2(L)3(H2O)6ꢀ6H2O]n (2)
A buffer layer of CH3OH/DMF (6 ml, 1:1) was carefully layered
over a water (4 ml) solution of Zn(OAc)2 (22 mg, 0.1 mmol). Then a
solution of H2L (35 mg, 0.1 mmol) in methanol (3 ml) was layered
Fig. 1. View of the metal coordination environment in 1 (H atoms are omitted for clarity).

Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
111
C, 49.75; H, 5.81. IR (cmꢁ1): 3411(s), 2915(w), 2832(w), 1639(s),
1526(m), 1445(s), 1337(m), 1255(m), 1086(m), 845(w), 773(s),
497(m).
(a)
2.2.3. [Pb2Na2(L)3(DMF)4(H2O)2ꢀ2H2O]n (3)
A
mixture of Pb(CH3COO)2ꢀ3H2O (0.379 g, 1 mmol), H2L
O
(0.344 g, 1 mmol) and NaOH (0.080 g, 2 mmol) were dissolved in
DMF (12 ml) and water (3 ml), the mixed solution was stirred at
60 °C for 3 h. Upon cooling to room temperature, the solution
was filtered and the filtrate was allowed to stand at room temper-
ature. After slow evaporation over 2 weeks, colorless acicular sin-
gle crystals were obtained. Yield: 60% based on Pb. Anal. Calcd.
for C69H90Na2Pb2N4O26: C, 44.75; H, 4.90; N, 3.02. Found: C,
43.93; H, 4.58; N, 3.42. IR (KBr, cmꢁ1): 3470(s), 2959(w),
2871(w), 1657(m), 1608(s), 1506(m), 1421(m), 1322(m), 1244(s),
1188(m), 1058(m), 832(s), 721(w), 532(w).
O
O
O
O
Cd
Cd
O
(b)
O
O
O
O
2.3. X-ray crystallography
Zn
Zn
O
O
X-ray single-crystal diffraction data for complexes 1–3 were
collected on a Bruker APEX-II area-detector diffractometer with
Mo K
a radiation (k = 0.71073 Å). Absorption corrections were ap-
(c)
plied by SADABS. All the structures were solved by direct methods
using the SHELXS program of the SHELXTL package and refined by
full-matrix least-squares methods with SHELXL [24]. Metal atoms
in each complex were located from the E-maps and other non-
hydrogen atoms were located in successive difference Fourier syn-
theses and refined with anisotropic thermal parameters on F2. The
hydrogen atoms of the ligand were generated theoretically onto
the specific atoms and refined isotropically with fixed thermal fac-
tors. The disordered groups of DMF molecules in 3 were split in
two positions in the refinement.
Na
O
O
O
O
Pb
Pb
O
O
Na
Na
(d)
Crystallographic data and experimental details for structural
analyses are summarized in Table 1. Selected bond lengths and an-
gles are listed in Table 2.
3. Results and discussion
Na
Na
O
O
O
O
3.1. Description of crystal structures
O
Pb
Pb
O
3.1.1. [Cd(L)(H2O)2]n (1)
Scheme 1. The coordination mode of L.
As illustrated in Fig. 1, each Cd(II) atom in 1 is coordinated by
six oxygen atoms from two chelating carboxylate groups of two
L ligands and two water molecules. The coordination sphere of
the Cd(II) center is best described as a trapezoidal bipyramid.
The O2, O3, O3A, O4A atoms define the equatorial plane. The axial
positions are occupied by O2A and O4 atoms with O2AACdAO4
on the buffer layer in a test tube. After 20 days, colorless block single
crystal appeared at the buffer layer were collected. Yield (based on
Zn): 30%. Anal. Calcd. for C57H78Zn2O30: C, 49.83; H, 5.72; Found:
Fig. 2. The 1D zig-zag chain structure of 1 viewed along the a-axis.

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Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
Fig. 3. Perspective view of the 3D supramolecular networks of complex 1.
angle of 141.9(3)°. Which is similar to the Cd(II) complex of phe-
noxyacetic acid [25].
3.1.2. [Zn2(L)3(H2O)6ꢀ6H2O]n (2)
As shown in Fig. 4, each Zn center located on the crystallo-
graphic 3-fold axis is coordinated by three water molecules and
three oxygen atoms of three distinct L ligands. The coordination
polyhedron of the Zn(II) atom can be viewed as distorted octahe-
dron. Each L ligand bridges two metal ions through two terminal
carboxylate groups in monodentate coordination mode (Scheme
1b). The Zn centers serve as 3-connected nodes in the framework,
thereby creating an infinite two-dimensional (6, 3) network, which
contains large edge-sharing hexagons with a metal ion at each cor-
ner and L ligand molecule at each edge (Fig. 5). The hexagonal grids
Each L ligand bridges two cadmium atoms in a chelating/chelat-
ing bis(bidentate) coordination mode (Scheme 1a) to form a 1D
infinite zig-zag chain (Fig. 2) along the a-axis with a Cdꢀ ꢀ ꢀCd dis-
tance of 14.065(3) Å. Interestingly, these chains are interlinked
by OAHꢀ ꢀ ꢀO hydrogen bonds produced by the L and coordinated
water molecules[O4ꢀ ꢀ ꢀO1A = 2.905 Å, O4ꢀ ꢀ ꢀO2A = 2.762 Å and
O4ꢀ ꢀ ꢀO3B = 2.623 Å, and the angles O4AH12ꢀ ꢀ ꢀO1A = 164.99°,
O4AH12ꢀ ꢀ ꢀO2A = 120.11°, O4AH11ꢀ ꢀ ꢀO3B = 110.18° symmetry
code A: x, y, zꢁ1; B: x, yꢁ1/2, zꢁ1/2] into a 3D network (Fig. 3).
Fig. 4. View of the metal coordination environment in 2 (H atoms and lattice water are omitted for clarity).

Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
113
Fig. 5. Perspective view of the 2D (6, 3) layer of complex 2, the H atoms and lattice water are omitted for clarity.
Fig. 6. Schematic representation of 2, showing the stacking of the noninterpenetrating (6, 3) networks. The lines represent ligand molecules.
exhibit identical edge lengths [17.56(1) Å] and identical corner an-
gles [71.06(1)°], and the separation of the opposite corner is
26.92(6) Å. Because of the length and flexibility of the L ligand,
the metal ions of (6, 3) network do not lie in the same plane but
represent a chair conformation.
It should be pointed out that, the 2D coordination networks of 2
do not interpenetrate each other, which is rare in such large
macrometallacycle frameworks [26,27]. In addition, in the crystal
structure such 2D layers are interlinked by OAHꢀ ꢀ ꢀO hydrogen
bonds [O4ꢀ ꢀ ꢀO2A = 2.856 Å and the angles O4AH12ꢀ ꢀ ꢀO2A =

114
Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
Fig. 7. Molecular structure of complex 3 with 30% probability ellipsoids. Hydrogen atoms are omitted for clarity.
132.93°, symmetry code A: ꢁy + 1, ꢁx + 1, zꢁ1/2] to finish the 3D
tances approximately 9 Å) (Fig. 9a). The square shaped channels
filled by the guest DMF and water molecules, and the hexagonal
channels are empty (Fig. 9b). The van der Waals free space of the
voids per unit cell (after the solvent water molecules have been
hypothetically removed) is approximately 2810 Å3, corresponding
to 37.0% of the volume of the unit cell (calculated by Platon)
[32].
From the topological point of view, the 3D structure of 3 can be
simplified to a unique (3, 4, 4, 5)-connected net with an unprece-
dented {42;6}2{42;83;10}{42;84}2{47;63}2 topology (Fig. 10)
[33,34]. In this simplification, the Pb(II) atom acts as the three-con-
nected node {42;6}2, the Na(I) atom acts as one kind of the four-
connected node {42;83;10}, the L ligands with a chelating-bridging
tridentate/chelating-bridging tridentate coordination mode as the
other four-connected node{42;84}2, and the other L ligands as
five-connected node{47;63}2.
stacking (Fig. 6).
3.1.3. [Pb2Na2(L)3(DMF)4(H2O)2ꢀ2H2O]n (3)
As shown in Fig. 7, the sodium ion was located in a distorted
octahedral coordination environment. The axis position was occu-
pied by a DMF and a carboxylate oxygen atom of L, respectively.
Three oxygen atoms from carboxyl groups of L and a water mole-
cule are in the equatorial positions. The Pb(II) ion is four-coordi-
nate with four carboxylate oxygen atoms from three different L
ligands and exhibits a tetrahedral geometry. The four oxygen
atoms are located on one side of the Pb(II) ion which adopts a
hemidirected structural categories and shows the presence of a
stereochemically active lone electron pair [28,29]. Indeed, when
the bonding limit of PbAO in complex 3 extends from 2.76 to
3.16 Å, the potential weak reactions (represented as dashed in
Fig. 7) are found. The five weak bonds in the direction of the void
complete the coordination sphere and increase the coordination
number of Pb(II) from four to nine. For all of the nine bonds around
Pb(II) are comparatively symmetrical, the coordination geometry
of Pb(II) in 3 can be viewed as holodirected [30,31].
3.2. Thermogravimetric analysis
Thermogravimetric analysis (TGA) for compounds 1–3 was per-
formed under a flow of N2 gas (Fig. 11). For compound 1, its TG
curve (Fig. 11a) shows three main steps of weight losses. The first
step started at 100 and completed at 130 °C, which corresponds to
the release of two coordination water molecules. The observed
weight-loss of 7.80% is close to the calculated value (7.34%). The
second and third steps (310–560 °C) corresponds to the release
of L ligands, giving cadmium oxides as the final decomposition
product which constitutes 26.54% (calcd. 26.17%). TG curve
(Fig. 11b) of 2 exhibits three steps of weight losses. The weight-loss
of 15.26% during the first and two steps from 50 to 150 °C corre-
sponds to the loss of six crystal-lattice water molecules and six
coordination water molecules (calcd. 15.74%). The third step
(330–550 °C) corresponds to the release of L ligands, giving ZnO
as the final decomposition product which constitute 12.46% (calcd.
11.85%).
In complex 3, the L ligands show two different coordination
modes. One is a pentadentate chelating and bridging coordination
mode (Scheme 1c), on the basis of this connection mode, the het-
erometallic ions Na(I) and Pb(II) were bridged by L ligands to form
a 2D layer of composition [Na2Pb2(L)2]n (Figs. 8a), which con-
structed by square shaped tubular channels (channel A with
dimensions of approximately 10 ꢂ 10 Å) edge-sharing the 1D me-
tal/carboxylate chains (Figs. 8b). The layers are further linked by
other L ligands in a chelating-bridging tridentate/chelating-bridg-
ing tridentate coordination mode (Scheme 1d) to generate a novel
3D channeled framework (Fig. 9). Which still have two other par-
allel tunnels except the square shaped channels mentioned above:
one square shaped (channel B with dimensions of approximately
10 ꢂ 10 Å) and one hexagonal (channel C with interatomic dis-

Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
115
Fig. 8. (a) Perspective view of the 2D supramolecular layer of composition [Na2Pb2(L)2]n. (b) Propagation in the c-direction of the chain, built up by the metals bridged by
carboxyl groups of L.
As shown in Fig. 11c, compound 3 loses all DMF and water mol-
ecules in the range 50–301 °C with a weight-loss of 19.11% (calcd.
19.68%). One L ligand is released in 347–434 °C with a weight-loss
of 19.25% (calcd. 18.47%), resulting in an intermediate product
[Na2Pb2(L)2] formed. This intermediate specie is further decom-
posed in 700–900 °C with a final residue Na2Pb2O3 formed (found
15.85%, calcd. 16.26%).
solution or hydrothermal reactions, and structurally character-
ized by X-ray diffraction analysis. These compounds show 1D,
2D and 3D coordination frameworks, respectively. The present
study demonstrates that the ‘‘V” shape L anion is capable of
coordination to metal centers in variable coordination modes,
and the MOFs exhibit different dimensionalities with different
metal ions, as well as that the coordination geometry of the
metal ions is very important for the formation of acentric crystal
4. Conclusions
structures.
Meanwhile,
the
intramolecular/intermolecular
hydrogen-bonding interaction, play an important role in
the formation of complexes, especially linking the discrete sub-
units or low-dimensional entities into high dimensional
frameworks.
Three coordination polymers of a ‘‘V” shape ligand 4,40-[iso-
propylidenebis(p-phenyleneoxy)diacetic acid (H2L) with the
Cd(II), Zn(II) and Pb(II) ions have been synthesized under room

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Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
Fig. 9. (a) View of the packing diagram along the c-direction, with the different channels presented, hydrogen atoms and solvent molecules are omitted for sake of clarity. (b)
View of the square column filled by the guest DMF and water molecules.
1, 744704 2 and 658570 3. Copies of these information may
be obtained free of charge on application to the Director, CCDC,
12 Union Road, Cambridge, CB2 1EZ, UK (Fax: +44 1223
336033; e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
Supplementary material
Crystallographic data (excluding structure factors) for the
structure analyses of complexes 1–3 have been deposited with
the Cambridge Crystallographic Data Center, CCDC No. 658571

Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
117
Fig. 10. Schematic illustration of the (3, 4, 4, 5)-connected 3D net. Color scheme: Pb, pink; Na, dark blue; L, pale blue. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this paper.)
Fig. 11. TG curves of compounds 1–3.

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Z.-B. Zheng et al. / Journal of Molecular Structure 964 (2010) 109–118
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