Synthesis, structure and properties of four new coordination polymers based on 2-(4-Chloro-phenoxy)-N-pyridin-3-ylacetamide

Article abstract of DOI:10.1016/j.poly.2016.10.029

A series of coordination polymers, namely, [Zn(L)(HIP)(H₂O)] (1), [Cd(L)(HIP)]·1/2H₂O (2), [Co_1.5(L)(BTC)(CH₃OH)(H₂O)₃]·2H₂O (3), [Ni_1.5(L)(BTC)(H₂O)₄]·3H₂O (4), where L = 2-(4-Chloro-phenoxy)-N-pyridin-3-ylacetamide, H₂HIP = 5-hydroxyisophthalic acid, H₃BTC = 1,3,5-benzenetricarboxylic acid, have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction analysis reveals that the complexes 1, 3 and 4 display 1D chain structure. In complex 2, each Cd₂unit is linked into BTC form two dimensional layer structures, which are further connected by μ₂-L ligand to construct 3D architecture with {4²⁴;6⁴}-bcu topology. Moreover, their powder X-ray diffraction analysis, thermostability and luminescence properties are explored.

Full text of DOI:10.1016/j.poly.2016.10.029

Accepted Manuscript
Synthesis, structure and properties of four new coordination polymers based on
2-(4-Chloro-phenoxy)-N-pyridin-3-ylacetamide
Shao-Yin Mo, Dong-Lin Fang, Bao-Yi Yu, Shi-Hua Tang
PII:
S0277-5387(16)30526-5
DOI:
http://dx.doi.org/10.1016/j.poly.2016.10.029
POLY 12282
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
21 August 2016
17 October 2016
19 October 2016
Please cite this article as: S-Y. Mo, D-L. Fang, B-Y. Yu, S-H. Tang, Synthesis, structure and properties of four new
coordination polymers based on 2-(4-Chloro-phenoxy)-N-pyridin-3-ylacetamide, Polyhedron (2016), doi: http://
dx.doi.org/10.1016/j.poly.2016.10.029
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Synthesis, structure and properties of four new
coordination polymers based on
2-(4-Chloro-phenoxy)-N-pyridin-3-ylacetamide
Shao-Yin Moa Dong-Lin Fanga Bao-Yi Yub and Shi-Hua Tanga*
a College of Chemistry and Chemical Engineering, Guangxi University for Nationalities,
Nanning, 530006, P.R. China, *E-mail: shtang5@sohu.com
b Beijing University of Agriculture, Beijing, 102206, P. R. China.
Abstract: A series of coordination polymers, namely, [Zn(L)(HIP)(H2O)] (1),
[Cd(L)(HIP)]·1/2H2O
[Ni1.5(L)(BTC
(2),
[Co1.5(L)(BTC)(CH3OH)(H2O)3]·2H2O
(3),
)(H2O)4]·3H2O (4), where L = 2-4-(Chloro-phenoxy)-N-pyridin-3-yl-acetamide,
H2HIP = 5-hydroxyisophthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid, have
been synthesized under hydrothermal conditions. Single crystal X-ray diffraction
analysis reveals that the complexes 1, 3 and 4 display 1D chain structure. In complex
2, each Cd2 unit is linked into BTC form two dimensional layer structures, which are
further connected by µ2-L ligand to construct 3D architecture with {424;64}-bcu
topology. Moreover, their power X-ray diffraction analysis, thermostability and
luminescence properties are explored.
Keywords: Coordination polymers Acylamide Multicarboxylate
Introduction
The construction of coordination polymers has attracted considerable interest during
the past decades not only due to their intriguing network topologies but also their
potential applications in catalysis[1,2], luminescence[3,4], magnetism[5], gas

adsorption[6,7], electrochemistry[8,9]. A large number of studies showed that the
synthesis of coordination frame works depend on reaction temperature, systematic pH
reactants, molar ratio, central metal ion, and the nature of organic ligands[10-14].
Especially properties of organic ligands, such as angle, distance, flexibility, and
functional groups, are the key factors for the synthesis of framework of coordination
polymers[15-18]. Therefore, utilizing multidentate organic ligands including N or O
donors is considered to be an effective strategy to form coordination polymers[19-20].
Acylamide functional ligands as N-donor ligands have been received widespread
attention because not only their has the abilities to provide two types of hydrogen
bonds sites, the -NH moiety acting as an electron acceptor and the -C=O group acting
as an electron donor, which is contribute to the construction of supramolecular
structure but also obtained product has a potential biological activity[21-25]. The
study of amide complexes including mono-pyridyl-mono-amide[26,27], pyridyl
mono-amide[27,28], bis-pyridyl-bis-amide[29-30] and tripyridyl tri-amide[31] has
attracted much attentions in recent years.
Multicarboxylate ligands as multidentate O-donor ligands such as
1,4-benzenedicarboxylic
acid
(1,4-H2BDC),
1,3,5-Benzenetricarboxylic
(1,3,5-H3BTC) are often selected as multifunctional organic linkers to form the
structures of higher dimensions because of their abundant coordination modes and
strong coordination ability[32-34]. A great number of 1D-, 2D-, 3D-framework,
constructed by combining the carboxylate ligands and N-donor ligands under
hydrothermal conditions, were reported[35]. For example, Wang's group reported a

series bis-pyridyl-bis-amide coordination polymers and their properties including
luminescence, electrochemistry and photocatalytic properties in recent years[36-38].
In this study, we chose the 2-(4-Chloro-phenoxy)-N-pyridin-3-yl-acetamide (L)
(Scheme 1) and 5-hydroxyisophthalic acid (H2HIP), 1,3,5-benzenetricarboxylic acid
(H3BTC) (Scheme 2) as mixed ligands to react with the transition metal salts and as a
result, four new complexes [Zn(L)(HIP)(H2O)] (1), [Cd(L)(HIP)]·1/2H2O (2),
[Co1.5(L)(BTC)(CH3OH)(H2O)3]·2H2O (3), [Ni1.5(L)(BTC)(H2O)4]·3H2O (4). Their
solid state structures, power X-ray diffraction analysis, thermal stability and
luminescent properties have been studied.
Experimental
All the reagents and the solvents were purchased commercially and were used
directly without further purification. Elemental analysis for C, H and N was carried
out on Perkin-Elmer 2400II elemental analyzer. The FT-IR spectrometer fourier
transform infrared spectroscopy in the 4000-400 cm-1 regions, using KBr pellets.
Perkin-Elmer Diamond TG/DTA thermal analyzer was used under atmosphere at a
heating rate of 10 K min-1 in the temperature range 25-800 using platinum crucibles.
Fluorescence spectra were recorded with F-2500 FL Spectrophotometer analyzer.
Powder X-ray diffraction patterns were obtained by using a pinhole camera (Anton
Paar) operating with a point focused Ni-filtered Cu Kα radiation in the 2θ range from
5° to 50° with a scan rate of 0.08° per second.

Synthesis of L
The L ligand was prepared according to the literature method[39]. Elemental
Anal. Calc. for C13H11ClN2O2: C 59.39, H 4.19, N 10.66. Found: C 59.37, H 4.20, N
10.67 %. IR (cm-1): 3445 (s), 1684 (s), 1650 (m), 1592 (m), 1537 (s), 1508 (w), 1489
(s), 1434 (m), 1408 (m), 1284 (m), 1235 (s), 1172 (w), 1089 (w), 1067 (m), 822 (m),
710 (m), 664 (m).
Synthesis of [Zn(L)(HIP)(H2O)] (1)
A mixture of Zn(NO3)2·6H2O (0.0297 g, 0.1 mmol), L (0.0263 g, 0.1 mmol),
H2HIP (0.0182 g, 0.1mmol), water (10 mL), and NaOH (0.010 g, 0.25 mmol) was
placed in a 25mL Teflon reactor. The mixture was heated at 120 for 3d, followed by
slow cooling to room temperature. The resulting orange crystalline materials were
collected. Yield: 42% (based on Zn). Elemental Anal. Calc. for C21H17ClN2O8Zn: C
47.89, H 3.23, N 5.32; found: C 47.87, H 3.21, N 5.35 %. IR (cm-1): 3382 (s), 3256
(s), 3065 (s), 1706 (m), 1629 (m), 1600 (w), 1566 (s), 1489 (s), 1446 (w), 1416 (m),
1364 (m), 1334 (m), 1311 (w), 1292 (w), 1243 (w), 1224 (m), 1127 (w), 1089 (m),
1003 (m), 820 (w), 782 (m), 735 (m) 665 (w).
Synthesis of [Cd(L)(HIP)]·1/2H2O (2)
A similar synthetic procedure was followed as that for 1. Here, a salt of
3CdSO4·8H2O (0.0256 g, 0.1mmol) was used. Orange crystalline material 2 were
gained. Yield: 40% (based on Cd). Elemental Anal. Calc. for C42H32Cl2N4O15Cd2: C
44.66, H 2.84, N 4.96; found: C 44.65, H 2.85, N 4.98 %. IR (cm-1): 3440 (s), 1669

(m), 1609(w), 1541 (s), 1488 (s), 1442 (w), 1421 (w), 1380 (m), 1269(m), 1241(m),
1191 (w), 1128 (w), 1063 (m), 808 (w), 783 (m), 735 (m), 694 (w).
Synthesis of [Co1.5(L)(BTC)(CH3OH)(H2O)3]·2H2O (3)
A mixture of Co(NO3)2·6H2O (0.0291 g, 0.1 mmol), L (0.0263 g, 0.1 mmol),
1,3,5-H3BTC (0.0210 g, 0.1 mmol), H2O (2 mL), CH3OH (2 ml) and NaOH (0.010 g,
0.25 mmol) was heated in a sealed glass tube at 85 for 3 days, then, the resulting
solution was cooled to room temperature, red prism-shaped crystalline material was
collected by filtration. Yield: 45% (based on Co). Elemental Anal. Calc. For
C46H56Cl2N4O28Co3: C 40.57 , H 4.12 , N 4.12; found: C 40.56, H 4.14, N 4.10 %. IR
(cm-1): 3286 (s), 1668 (m), 1610 (s), 1547 (s), 1489 (m), 1460 (w), 1431 (m), 1372 (s),
1285 (w), 1247 (m), 1168 (w), 1094 (w), 1069 (w), 1010 (m), 827 (w), 808 (w), 761
(m), 715 (m).
Synthesis of [Ni1.5(L)(BTC)(H2O)4]·3H2O (4)
A similar synthetic procedure was followed as that for 1. Here, a salt of
Ni(CH3COO)2·4H2O (0.0249 g, 0.1 mmol) was used and H2HIP was replaced by
H3BTC (0.0210 g, 0.1 mmol). The resulting green crystalline material were collected.
Yield: 38% (based on Ni). Elemental Anal. Calc. For C44H42Cl2N4O30Ni3: C 38.60, H
4.09, N 4.09; found: C 38.63, H 4.07, N 4.12 %. IR (cm-1): 3384 (s), 1666 (m), 1611
(s), 1548 (s), 1530 (s), 1489 (s), 1461 (w), 1430 (s), 1369 (s), 1284 (w), 1246 (m),
1169 (w), 1095 (w), 1070 (w), 1009 (w), 827 (w), 812 (w), 761 (m), 718 (m).

Description of crystal structures
[Zn(L)(HIP)(H2O)] (1)
Single-crystal X-ray diffraction analysis reveals that complex 1 crystallized in
the triclinic space group P-1. The crystal structure of complex 1 contains a Zn ion,
one L ligands and two HIP anions and one coordinated water. As shown in Fig. 1a,
each ion adopts a distorted {ZnNO3} tetrahedral geometry to coordinate with one
nitrogen atom from one L ligand with a Zn-N2 distance of 2.047(3) Å, Three oxygen
atoms from the two HIP ligands and one coordinated water molecule, with the Zn-O
distances of 1.952(3) Å, 2.000(3) Å and 2.011(3) Å, respectively. In 1, the HIP anion
shows a similar “V” shaped bis(monodentate) bridging coordination mode to connect
the adjacent Zn(1) ions to form a chain with a Zn···Zn 9.467(5) distance of Å. The
adjacent 1D chains are also linked together by the hydrogen bonding interaction
between the oxygen atoms of coordinated water molecule and HIP
[O(8)-H(8A)···O(2)#4 ], this forms a ladder-like 2D supramolecular net (Fig. 1b). The
final 3D supramolecular framework of 1 is constructed through the hydrogen bonding
interactions (O(8)-H(8B)...O(7)#3 = 2.649(4) Å, N(1)-H(1)...O(3)#3 = 2.851(4) Å,
O(5)-H(5)...O(4)#5 = 2.800(4) Å) (fig. 1c).
[Cd(L)(HIP)]·1/2H2O (2)
Single crystal X-ray crystallography reveals that complex 2 is a 3D metal
-organic coordination polymer. The coordination environment of Cd ion is depicted in
Fig. 2a. The Cd ion is coordinated by four oxygen atoms [Cd(1)-O, 2.2086(17)
-2.4537(18) Å] from three HIP ligands, which occupy equatorial positions and one

nitrogen atom (N2A) as well as oxygen atom (O6) from two L ligands [Cd(1)-N(2)#3
= 2.311(2) Å, Cd(1)-O(6) = 2.451(2) Å] , which belong to axial positions, which
construct a six-coordinated octahedron environment. As for the HIP ligands, all the
hydroxyl groups do not participate in the coordination with Cd ions but the two
carboxylate groups of the HIP ligands adopt different coordination fashion to connect
Cd ions. One carboxylate group connects to Cd(II) ion, and another carboxylate group
adopts a chelate / bridge tridentate coordination mode connecting two Cd(II) ions (Fig.
2b). Two Cd (II) ions are linked by two chelate / bridge carboxylate groups from two
HIP to form a Cd2 unit with a Cd ··· Cd separation of 3.738 Å. Different Cd2 units are
connected by µ2 - HIP resulting in a 2D layer with 44-sql. Different 2D layers are
linked by µ2 - L ligands to form a 3D architecture (fig. 2c).
Each Cd2 unit is linked by four ligands and four HIP anions, which can be
defined as an 8-connected node. Topologiacal analysis reveals that it is a uninodal
8-connected noninterpenetrated network with {424;64}-bcu topology (fig. 2d).
[Co1.5(L)(BTC)(CH3OH)(H2O)3]·2H2O (3) and [Ni1.5(L)(BTC)(H2O)4]·3H2O (4)
Complex 4 show a similar coordination environment as complex 3, complex 3
contains one coordinated methanol molecule and there is one coordinated water
molecules on the structure of complex 4. complex 3 and complex 4 crystallizes in the
triclinic space group P-1, The asymmetric unit of 3 contains one and a half Co(II)
atoms, one L ligand, one BTC ligand, three coordinated water molecules, one
coordinated methanol molecule and two lattice water molecules. As show in Fig. 3a,
there are two crystallographically independent Co(II) centers with same coordination

environments, the Co1 is six-coordinated by two oxygen atoms from carboxylate
groups of two BTC ligand in the apical positions and four coordinated water
molecules in the equatorial positions showing a CoO6 distorted octahedral
environment. The Co2 is surrounded by five oxygen atoms of two carboxyl groups
from one BTC ligand, one coordinated methanol molecule and one coordinated water
molecules as well as one nitrogen atom from L. In 3, The BTC ligands adopt a µ3-
bridging mode connect with three Co(II) ions to generate a ladder-like chain with the
Co1 on the rungs (Co1···Co1 10.352 Å), and the Co2 on the siderails (Co2···Co2
10.352 Å). The ladder-like chain are further connected by hydrogen bonding
interaction (O(2W)-H(2W1)...O(8)#5), resulting in a 2D network of complex 3 (Fig.
3b). Finally, coordinated water molecules connect the adjacent layers into 3D
supramolecular
framework
by
hydrogen
bonding
interactions
(O(2W)-H(2W2)...O(3)#4, O(2W)-H(2W1)...O(8)#5) (Fig. 3c).
IR spectrum
The strong peaks at 1629 and 1334 cm-1 for 1, 1609 and 1380 cm-1 for 2, 1610
and 1372 cm-1 for 3, 1611 and 1369 cm-1 for 4, may be attributed to the asymmetric
and symmetric vibrations of carboxyl groups. The bands around 1706 cm-1 for 1 and
1669 cm-1 for 2, 1668 cm-1 for 3, 1666 cm-1 for 4, are characteristic of the carbonyl
groups. The presence of the characteristic bands at 1566, 1489, 1446, 1364 cm-1 for 1,
1541, 1488, 1442, 1421 cm-1 for 2, 1547, 1489, 1460, 1431 cm-1 for 3, 1548, 1489,
1461, 1430 cm-1 for 4, suggest the stretching vibrations of the pyridyl rings the

organic ligands. The bands at 3382 3440 3286 3384 are assigned to stretching and
bending vibrations of -OH groups of water molecules for complex 1-4.
Fluorescent properties
The samples for solid-state luminescence of complexes 1-2 and the free ligand L
have been investigated at room temperature because of their potential photoactive
applications[40]. As show in Fig. 5, the L ligand displays an emission band at 312 nm
(λex = 276 nm), which may be ascribed to the π → π* or n → π* transitions[41].
Under the same excitation conditions, the complex 1 displays a broad and strong
emission at 368 nm upon excitation at 273 nm. For complex 2, it can be observed that
emission occurs at 344 nm (λex = 271 nm). Thus, compared to L, the emission maxima
of 1 and 2 are red-shifted. The most likely emission mechanism is ligand-to-metal
charge transfer (LMCT)[42]. The fluorescent intensity of complex 1 is stronger than
that of the free ligand, because of the ligand coordinated to the metal center, which
enhances its rigidity and thus reduces the loss of energy through radiationless
pathways[43]. The strong fluorescence emission of complex 1 show a potential
application value in photosensitive material.
Thermogravimetric analyses
Thermal gravimetric analyses (TGA) of coordination complexes 1-4 investigated
to exhibit their thermal stabilities. As shown in Fig. 6, the test for complexes 1-4 are
carried out at temperature range from 30 to 800 under an air atmosphere, For 1, the
first weight loss, 5.08 %, at 130-175
is ascribed to a loss of coordinated water
molecules (Calc. 3.42 %). The overall framework of 1 begins to collapse at 280 and

ends 600
2.11 % for 2 at a region of 140-280 is equivalent to the elimination of the one water
molecule (Calcd: 1.60 %). The second stage occurs between 350 and 520 and
with the ZnO residue of 16.13 (Calcd: 15.47%). A first weight loss of
corresponds to the release of the organic ligand. The corresponding weight losses are
75.28 % (calcd. 75.64 %). After 520 , there is no further weight loss. The residues
(22.61 %) is CdO (Calcd. 22.76 %). For complex 3, the first weight loss step from
90-210 is attributed to the loss of the lattice water, coordinated water molecules and
methanol molecules. The weight loss is about 17.20 % (Calcd. 17.94 %). A second
weight loss was observed in a range of 210-550
, corresponding to the
decomposition of organic ligands L and BTC. The CoO residue of 3 of 17.73 % (calcd:
16.52 %). The TG curves of complex 4 exhibit two obvious weight loss steps. The
first weight loss of 14.72 % at timeperatures between 80 and 200 is assigned to the
elimination of the water molecules and coordinated waters (calcd.: 17.76 %). The
second weight loss occurred at 270 . The NiO residue of 4 is 16.68 % (calcd:
16.38 %).
XRD Patterns
The observed and simulated power XRD patterns of the complexes 1-4 are
depicted in Fig. 6. It shows that the measured power XRD patterns are in good
agreement with the pattern simulated from the X-ray single-crystal data, indicating
phase purities of the sample.
Conclusion
In summary, a series of mono-pyridyl-mono-amide coordination polymers were

prepared under solvothermal conditions and were characterized by IR spectrum,
elemental analysis, fluorescent properties, thermogravimetric analysis and Powder
X-ray diffraction patterns analysis. The title complexes 1,3,4 display 1-D coordinated
polymer while complex 2 displays 3-D mof structure. The results show that
mono-pyridyl-mono-amide is a good candidate for construction coordination
polymers with stable and intriguing structures. Moreover, the polycarboxylates also
greatly contribute to the structural diversities of the final frameworks. The fluorescent
behaviors 1-2 imply that complexes 1 may be good candidates for photoactive
materials.
Appendix A. Supplementary data
CCDC 1486621 148662 1486624 1486625 contains the supplementary
crystallographic data for 1-4. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail:deposit@ccdc.cam.ac.uk.
Acknowledgments
The authors thank the National Natural Science Foundation of China (21267003),
PR China, the Natural Science Foundation of Guangxi (053020), P.R. China and
Guangxi University for Nationalities.

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Wang and W. Y. Sun, Cryst, Growth Des. 9 (2009) 2801.
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38 (2009) 1330.
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Z. Shi and S. H. Feng. CrystEngComm. 17 (2015) 5054.

Table 1 Crystallographic data for polymers 1-4
Polymer
Formula
1
2
3
4
C21H17ClN2O8Zn
C42H32Cl2N4O15Cd C46H56Cl2N4O28Co3 C44H42Cl2N4O30Ni3
2
Formula weight
Crystal system
Space group
a (Å)
526.19
Triclinic
P-1
1128.42
Orthorhombic
Pbcn
1360.64
Triclinic
P-1
1353.85
Triclinic
P-1
9.467(5)
10.054(6)
12.908(7)
68.421(7)
86.363(7)
69.873(7)
1.633
13.3967(19)
18.103(3)
17.019(2)
90
10.352(5)
10.788(5)
13.633(7)
112.299(6)
100.196(6)
93.932(5)
1.638
10.218(5)
10.777(5)
13.625(6)
112.644(5)
100.317(5)
94.339(5)
1.672
b (Å)
c (Å)
α (°)
90
β (°)
γ (°)
Dcalc. (Mg·m-3)
90
1.816
2
4
1
1
Z
Absorption
coefficient (mm-1)
F(000)
1.325
1.239
1.090
1.238
536
2248
699
692
Crystal size (mm3) 0.19 x 0.18 x 0.17
0.21 x 0.20 x 0.18
1.89 to 28.56
25230
0.14 x 0.13 x 0.12
1.65 to 25.00
7323
0.12 x 0.11 x 0.10
1.66 to 25.00
7310
1.70 to 26.00
5964
θ range (°)
Reflections
collected
Unique reflections
4070 [R(int) =
0.0406]
4960 [R(int) =
0.0249]
4746 [R(int) =
0.0173]
4679 [R(int) =
0.0187]
96.7 %
94.2 %
98.2 %
98.7 %
Completeness to θ
= 25.00
Max. and min.
transmission
Data / restraints /
parameters
0.8061 and 0.7868
4070 / 0 / 307
0.8078 and 0.7809
4960 / 0 / 299
0.8804 and 0.8624
4746 / 17 / 413
0.8862 and 0.8656
4679 / 2 / 384
GOF on F2
1.066
1.106
1.099
1.138
R1 = 0.0652,
wR2 = 0.1683
R1 = 0.0278 ,
wR2 = 0.0743
R1 = 0.0339 ,
wR2 = 0.0776
0.880 and-0.317
R1 = 0.0316, wR2
= 0.0945
R1 = 0.0319, wR2
= 0.0941
R indices [I >
2σ(I)]
R indices (all data) R1 = 0.0758,
R1 =0.0357 ,
wR2 = 0.0966
0.388 and -0.306
R1 = 0.0350, wR2
= 0.1011
wR2 = 0.1761
Largest diff. peak
and hole (e.Å-3)
1.797 and -1.476
0.751 and -0.389

Table 2 Selected bond lengths (Å) and angles (°) for 1-4
1
Zn(1)-O(6)#1
Zn(1)-O(3)
1.952(3)
O(6)#1-Zn(1)-C(21)#1
O(3)-Zn(1)-C(21)#1
O(8)-Zn(1)-C(21)#1
N(2)-Zn(1)-C(21)#1
C(14)-O(3)-Zn(1)
28.45(11)
137.07(11)
105.73(11)
111.08(12)
114.6(2)
2.000(3)
Zn(1)-O(8)
2.011(3)
Zn(1)-N(2)
2.047(3)
O(6)-Zn(1)#2
O(6)#1-Zn(1)-O(3)
O(6)#1-Zn(1)-O(8)
O(3)-Zn(1)-O(8)
O(6)#1-Zn(1)-N(2)
O(3)-Zn(1)-N(2)
O(8)-Zn(1)-N(2)
2
1.952(3)
108.77(11)
113.69(13)
96.25(11)
131.12(13)
99.85(12)
101.19(13)
C(21)-O(6)-Zn(1)#2
C(13)-N(2)-Zn(1)
C(12)-N(2)-Zn(1)
104.4(2)
116.2(3)
124.8(3)
74.0(2)
O(7)-C(21)-Zn(1)#2
O(6)-C(21)-Zn(1)#2
47.11(17)
Cd(1)-O(3)#1
Cd(1)-O(4)
2.2086(17)
2.2870(17)
2.2895(16)
2.311(2)
O(4)-Cd(1)-O(6)
80.82(8)
O(5)#2-Cd(1)-O(6)
N(2)#3-Cd(1)-O(6)
O(3)#1-Cd(1)-O(5)
O(4)-Cd(1)-O(5)
100.55(8)
167.49(8)
158.69(7)
54.73(6)
Cd(1)-O(5)#2
Cd(1)-N(2)#3
Cd(1)-O(6)
2.451(2)
Cd(1)-O(5)
2.4537(18)
2.2086(17)
2.2895(16)
2.311(2)
O(5)#2-Cd(1)-O(5)
N(2)#3-Cd(1)-O(5)
O(6)-Cd(1)-O(5)
76.04(6)
O(3)-Cd(1)#4
O(5)-Cd(1)#2
N(2)-Cd(1)#5
O(3)#1-Cd(1)-O(4)
O(3)#1-Cd(1)-O(5)#2
O(4)-Cd(1)-O(5)#2
99.97(7)
80.55(7)
C(21)-O(3)-Cd(1)#4
C(14)-O(4)-Cd(1)
C(14)-O(5)-Cd(1)#2
C(14)-O(5)-Cd(1)
102.30(14)
96.03(14)
167.74(16)
87.94(13)
136.85(6)
92.35(6)
130.06(6)
O(3)#1-Cd(1)-N(2)#3
O(4)-Cd(1)-N(2)#3
O(5)#2-Cd(1)-N(2)#3
O(3)#1-Cd(1)-O(6)
3
98.15(8)
89.25(7)
91.66(7)
84.19(7)
Cd(1)#2-O(5)-Cd(1)
C(8)-O(6)-Cd(1)
103.95(6)
155.1(2)
C(13)-N(2)-Cd(1)#5
C(12)-N(2)-Cd(1)#5
114.14(17)
127.49(18)
Co(1)-O(5)
2.0751(18)
2.0751(18)
2.0849(18)
2.0849(19)
2.1400(19)
2.1400(19)
2.0615(17)
2.064(2)
O(5)#1-Co(1)-O(2W)
O(1W)-Co(1)-O(2W)
O(1W)#1-Co(1)-O(2W)
O(5)-Co(1)-O(2W)#1
O(5)#1-Co(1)-O(2W)#1
O(1W)-Co(1)-O(2W)#1
89.11(7)
93.77(8)
86.23(8)
89.11(7)
90.89(7)
86.23(8)
Co(1)-O(5)#1
Co(1)-O(1W)
Co(1)-O(1W)#1
Co(1)-O(2W)
Co(1)-O(2W)#1
Co(2)-O(1)#2
Co(2)-O(3W)
Co(2)-O(7)
O(1W)#1-Co(1)-O(2W)#1 93.77(8)
O(2W)-Co(1)-O(2W)#1
O(1)#2-Co(2)-O(3W)
O(1)#2-Co(2)-O(7)
O(3W)-Co(2)-O(7)
O(1)#2-Co(2)-O(4)
O(3W)-Co(2)-O(4)
180.0
2.0912(18)
2.1343(17)
2.151(2)
89.75(7)
94.57(7)
89.98(7)
104.63(7)
95.02(7)
Co(2)-O(4)
Co(2)-N(2)
Co(2)-O(3)
2.2151(18)
2.0615(17)
O(1)-Co(2)#3

O(5)-Co(1)-O(5)#1
O(5)-Co(1)-O(1W)
O(5)#1-Co(1)-O(1W)
O(5)-Co(1)-O(1W)#1
180.0
O(7)-Co(2)-O(4)
O(1)#2-Co(2)-N(2)
O(3W)-Co(2)-N(2)
O(7)-Co(2)-N(2)
O(4)-Co(2)-N(2)
O(1)#2-Co(2)-O(3)
O(3W)-Co(2)-O(3)
O(7)-Co(2)-O(3)
N(2)-Co(2)-O(3)
160.15(6)
90.34(7)
178.42(7)
91.59(7)
83.43(7)
164.46(6)
87.59(7)
100.74(6)
91.91(7)
89.85(7)
90.15(7)
90.15(7)
O(5)#1-Co(1)-O(1W)#1 89.85(7)
O(1W)-Co(1)-O(1W)#1 180.0
O(5)-Co(1)-O(2W)
O(4)-Co(2)-O(3)
90.89(7)
60.41(6)
4
Ni(1)-O(7)#1
2.0285(19)
2.0285(19)
2.0645(19)
2.0645(19)
2.099(2)
O(3)-Ni(2)-O(9)
89.70(8)
Ni(1)-O(7)
O(10)-Ni(2)-O(9)
O(3)-Ni(2)-N(2)
88.81(8)
Ni(1)-O(11)
91.53(8)
Ni(1)-O(11)#1
Ni(1)-O(12)#1
Ni(1)-O(12)
O(10)-Ni(2)-N(2)
O(9)-Ni(2)-N(2)
91.91(8)
178.50(8)
101.70(8)
161.96(7)
93.42(8)
2.099(2)
O(3)-Ni(2)-O(6)#2
O(10)-Ni(2)-O(6)#2
O(9)-Ni(2)-O(6)#2
N(2)-Ni(2)-O(6)#2
O(3)-Ni(2)-O(5)#2
O(10)-Ni(2)-O(5)#2
O(9)-Ni(2)-O(5)#2
N(2)-Ni(2)-O(5)#2
O(6)#2-Ni(2)-O(5)#2
O(3)-Ni(2)-C(21)#2
O(10)-Ni(2)-C(21)#2
O(9)-Ni(2)-C(21)#2
N(2)-Ni(2)-C(21)#2
O(6)#2-Ni(2)-C(21)#2
O(5)#2-Ni(2)-C(21)#2
C(14)-O(3)-Ni(2)
C(21)-O(5)-Ni(2)#3
C(21)-O(6)-Ni(2)#3
C(22)-O(7)-Ni(1)
C(10)-N(2)-Ni(2)
C(11)-N(2)-Ni(2)
Ni(2)-O(3)
2.0237(18)
2.045(2)
Ni(2)-O(10)
Ni(2)-O(9)
2.053(2)
85.49(8)
Ni(2)-N(2)
2.078(2)
162.44(7)
101.01(7)
87.20(7)
91.36(7)
Ni(2)-O(6)#2
2.0957(19)
2.1791(19)
2.1791(19)
2.0957(19)
180.0
Ni(2)-O(5)#2
O(5)-Ni(2)#3
O(6)-Ni(2)#3
61.29(7)
O(7)#1-Ni(1)-O(7)
O(7)#1-Ni(1)-O(11)
O(7)-Ni(1)-O(11)
O(7)#1-Ni(1)-O(11)#1
O(7)-Ni(1)-O(11)#1
O(11)-Ni(1)-O(11)#1
O(7)#1-Ni(1)-O(12)#1
O(7)-Ni(1)-O(12)#1
O(11)-Ni(1)-O(12)#1
132.38(8)
131.39(8)
92.48(8)
89.33(7)
90.67(7)
90.67(7)
86.06(8)
89.33(7)
30.68(7)
180.000(1)
90.75(8)
30.74(7)
126.48(15)
87.50(13)
91.35(15)
132.10(16)
122.01(17)
119.93(18)
57.97(12)
61.76(12)
171.66(17)
89.25(8)
86.64(9)
O(11)#1-Ni(1)-O(12)#1 93.36(9)
O(7)#1-Ni(1)-O(12)
O(7)-Ni(1)-O(12)
89.25(8)
90.75(8)
93.36(9)
86.64(9)
180.000(1)
96.20(8)
O(11)-Ni(1)-O(12)
O(11)#1-Ni(1)-O(12)
O(12)#1-Ni(1)-O(12)
O(3)-Ni(2)-O(10)
O(6)-C(21)-Ni(2)#3
O(5)-C(21)-Ni(2)#3
C(19)-C(21)-Ni(2)#3
Symmetry transformations used to generate equivalent atoms: for Polymer 1: #1 x+1,y,z #2 x-1,y,z; for Polymer
2: #1 -x+1/2,-y+1/2,z-1/2 #2 -x+1,y,-z+1/2 #3 -x+1/2,y-1/2,z #4 -x+1/2,-y+1/2,z+1/2 #5 -x+1/2,y+1/2,z; for
Polymer 3: #1 -x+1,-y,-z+1 #2 x+1,y,z #3 x-1,y,z #4 x,y-1,z #5 -x+2,-y+1,-z+2 #6 -x+1,-y+1,-z+1 #7
-x,-y+1,-z+1 #8 x-1,y,z-1; for Polymer 4: #1 -x+1,-y+2,-z+1 #2 x+1,y,z #3 x-1,y,z #4 x,y+1,z #5 -x+1,-y+1,-z

#6 x+1,y-1,z #7 -x+1,-y+1,-z+1 #8 -x+2,-y+1,-z+1.
Table 3 Hydrogen-bond geometry (Å) for polymers 1-4
D-H···A
D-H
H···A D···A
D-H···A
Symmetry codes
Polymer 1
O(8)-H(8B)...O(7)#3
O(8)-H(8A)...O(2)#4
N(1)-H(1)...O(3)#3
O(5)-H(5)...O(4)#5
Polymer 2
0.89(8)
0.80(5)
0.86
1.84(8)
1.96(5)
1.99
2.649(4)
152(7)
165(5)
177.8
170.7
#1 x+1,y,z; #2 x-1,y,z
#3 -x+1,-y+2,-z
#4 x,y+1,z
2.739(4)
2.851(4)
2.800(4)
0.82
1.99
#5 -x+1,-y+2,-z+1
N(1)-H(1A)...O(7)
0.86
2.08
2.551(3)
113.8
#1 -x+1/2,-y+1/2,z-1/2
#2 -x+1,y,-z+1/2
#3 -x+1/2,y-1/2,z
O(1)-H(1)...O(2)#6
O(1)-H(1)...O(4)#7
0.82
0.82
2.40
2.47
3.171(3)
2.903(3)
157.7
114.1
#4 -x+1/2,-y+1/2,z+1/2
#5 -x+1/2,y+1/2,z
#6 -x+1,y,-z+3/2
O(8)-H(8A)...O(2)#6
1.03(7)
2.03(7)
3.049(4)
172(7)
#7 x+1/2,-y+1/2,-z+1
Polymer 3
O(1W)-H(1W1)...O(2)#4
O(1W)-H(1W2)...O(6)
O(2W)-H(2W1)...O(8)#5
O(2W)-H(2W2)...O(3)#4
O(3W)-H(3W1)...O(6)#6
0.848(10) 1.883(12) 2.720(3)
0.846(10) 1.939(13) 2.742(3)
0.853(10) 2.161(11) 3.011(3)
0.842(10) 2.019(10) 2.860(2)
0.842(10) 1.918(10) 2.758(3)
169(3)
#1 -x+1,-y,-z+1
#2 x+1,y,z
158(3)
175(3)
177(3)
177(3)
174(3)
166(4)
170(4)
178(4)
159(4)
163(3)
158(3)
#3 x-1,y,z
#4 x,y-1,z
#5 -x+2,-y+1,-z+2
#6 -x+1,-y+1,-z+1
#7 -x,-y+1,-z+1
O(3W)-H(3W2)...O(5W)#2 0.843(10) 1.921(11) 2.761(3)
O(4W)-H(4W1)...O(5W)#7 0.861(10) 2.052(15) 2.896(4)
O(4W)-H(4W2)...O(6)
O(5W)-H(5W1)...O(4)#6
O(5W)-H(5W2)...O(8)#8
O(7)-H(7)...O(2)#2
N(1)-H(1)...O(4W)#2
Polymer 4
0.859(10) 2.348(14) 3.198(3)
0.849(10) 1.930(10) 2.779(3)
0.843(10) 2.418(19) 3.218(4)
0.848(10) 1.821(13) 2.644(2)
0.850(10) 2.247(16) 3.052(3)
O(13)-H(13D)...O(15)#3 0.86(2)
2.15(10)
2.07
2.903(5)
2.919(3)
2.970(3)
2.705(3)
2.738(4)
2.779(3)
2.826(3)
2.713(3)
3.138(4)
2.535(3)
2.911(3)
2.676(3)
3.028(3)
2.657(3)
147(16) #1 -x+1,-y+2,-z+1
O(12)-H(12E)...O(5)#4
O(12)-H(12D)...O(2)#5
O(11)-H(11C)...O(4)#4
0.85
0.85
0.85
177.5
177.6
174.3
176.0
178.9
178.8
167(7)
154.6
111.7
115.5
174.5
118.9
176.2
#2 x+1,y,z
2.12
#3 x-1,y,z
1.86
#4 x,y+1,z
O(10)-H(10D)...O(14)#6 0.85
1.89
#5 -x+1,-y+1,-z
#6 x+1,y-1,z
#7 -x+1,-y+1,-z+1
#8 -x+2,-y+1,-z+1
O(9)-H(9D)...O(13)#7
O(9)-H(9C)...O(8)#8
O(13)-H(13C)...O(6)
N(1)-H(1)...O(15)
0.85
0.85
0.84(2)
0.86
0.86
0.85
0.85
0.85
0.85
1.93
1.98
1.89(3)
2.34
N(1)-H(1)...O(1)
2.09
O(11)-H(11D)...O(7)
O(11)-H(11D)...O(8)
O(10)-H(10E)...O(3)
O(10)-H(10E)...O(4)
2.44
1.83
2.53
1.81

Scheme 1. Structure of the L = 2-(4-Chloro-phenoxy)-N-pyridin-3-yl-acetamide (L)
ligand.
Scheme 2. Structrue of the carboxylic acids in this work.

Figure captions:
Fig. 1. (a) Coordination environment around the Zn(II) centers in 1. All the hydrogen
atoms are omitted for clarity; (b) two-dimensional polymeric frameworks of polymer
1; (c) The 3D structure of polymer 1.
Fig. 2. (a) Coordination environment around the Cd(II) centers in 2. All the hydrogen
atoms are omitted for clarity; (b) The layer constructed by Cd(II) atoms and HIP
ligands; (c) The 3D structure of polymer 2; (d) The{424;64}-bcu topology of polymer
2.
Fig. 3. (a) Coordination environment around the Co(II) centers in 3. All the hydrogen
atoms are omitted for clarity; (b) two-dimensional supramolecular framework of
polymer 3; (c) The 3D supramolecular framework of polymer 3.
Fig. 4. The solid-state fluorescence spectra of complexes 1-2 and the free ligand L at
room temperature.
Fig. 5. The TG curves for polymers 1-4.
Fig. 6. XRD patterns of the complexes 1-4.

(a)
(b)

(c)
Fig. 1. (a) Coordination environment around the Zn(II) centers in 1. All the
hydrogen atoms are omitted for clarity; (b) two-dimensional supramolecular
framework of polymer 1; (c) The 3D supramolecular framework of polymer 1.
(a)

(b)
(c)
(d)
Fig. 2. (a) Coordination environment around the Cd(II) centers in 2. All the
hydrogen atoms are omitted for clarity; (b) The layer constructed by Cd(II) atoms and
HIP ligands; (c) The 3D structure of polymer 2; (d) The{424;64}-bcu topology of
polymer 2.

(a)
(b)
(c)

Fig. 3. (a) Coordination environment around the Co(II) centers in 3. All the
hydrogen atoms are omitted for clarity; (b) two-dimensional supramolecular
framework of polymer 3; (c) The 3D supramolecular framework of polymer 3.
Fig. 4. The solid-state fluorescence spectra of complexes 1-2 and the free ligand L at
room temperature.

Fig. 5. The TG curves for polymers 1-4.
Fig. 6. XRD patterns of the complexes 1-4.

A
series of coordination polymers, namely, [Zn(L)(HIP)(H2O)] (1),
[Cd(L)(HIP)]·1/2H2O
[Ni1.5(L)(BTC
(2),
[Co1.5(L)(BTC)(CH3OH)(H2O)3]·2H2O
(3),
)(H2O)4]·3H2O (4), where L = 2-4-(Chloro-phenoxy)-N-pyridin-3-yl-acetamide,
H2HIP = 5-hydroxyisophthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid, have
been synthesized under hydrothermal conditions. Single crystal X-ray diffraction
analysis reveals that the complexes 1, 3 and 4 display 1D chain structure. In complex
2, each Cd2 unit is linked into BTC form two dimensional layer structures, which are
further connected by µ2-L ligand to construct 3D architecture with {424;64}-bcu
topology.