Syntheses and characterization of inorganic-organic hybrids with 4-(isonicotinamido)phthalate and some divalent metal centers

Article abstract of DOI:10.1016/j.poly.2010.05.014

Four new inorganic?organic hybrid frameworks [Mn(L)(H₂O) ₂]_n (1), {[Co(L)(H₂O)₃] ·2H₂O·CH₃OH}_n (2), {[Zn(L)(H ₂O)]·H₂O}_n (3) and [Cd(H

Full text of DOI:10.1016/j.poly.2010.05.014

Polyhedron 29 (2010) 2454–2461
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Syntheses and characterization of inorganic–organic hybrids with
4-(isonicotinamido)phthalate and some divalent metal centers
Man-Sheng Chen a,b, Qin Hua a, Zheng-Shuai Bai a, Taka-aki Okamura c, Zhi Su a,
c
Wei-Yin Sun a, , Norikazu Ueyama
*
a Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of
Microstructure, Nanjing University, Nanjing 210093, China
b Department of Chemistry and Materials Science, Hengyang Normal University, Hengyang 421008, China
c Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Four new inorganic–organic hybrid frameworks [Mn(L)(H2O)2]n (1), {[Co(L)(H2O)3]ꢀ2H2OꢀCH3OH}n (2),
{[Zn(L)(H2O)]ꢀH2O}n (3) and [Cd(HL)2]n (4) [H2L = 4-(isonicotinamido)phthalic acid] have been synthe-
sized and characterized by single-crystal X-ray diffraction analysis. Complex 1 has three-dimensional
(3D) structure and topology related to SrAl2 (sra) with Schläfli symbol of (42ꢀ63ꢀ8). And 2 displays
(3,3)-connected two-dimensional (2D) network with (4,82) topology, while 3 exhibits a uninodal (3,3)-
connected (6,3) 2D network, which is further linked by N–Hꢀ ꢀ ꢀO hydrogen bonding interactions to give
3D structure with hms topology and Schläfli symbol of (63)(69ꢀ8). Complex 4 with partial deprotonated
HLꢁ ligands also has a 2D network structure. In addition, the magnetic property of 1, nonlinear optical
property of 3 and photoluminescence of 3 and 4 were investigated.
Received 19 January 2010
Accepted 19 May 2010
Available online 26 May 2010
Keywords:
Inorganic–organic hybrid framework
Magnetic property
Nonlinear optical property
Photoluminescence property
Topology
Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
the influence of metal ions on the structure of metal–organic
frameworks. In addition, the magnetic property of 1, nonlinear
The coordination chemistry of transition metal–carboxylate has
attracted great interests of chemists not only because of their fas-
cinating structural diversities, but also due to their interesting
properties and potential applications as functional materials in dif-
ferent fields [1–12]. The reported studies showed that the carbox-
ylate groups can adopt varied coordination modes, and as a result
metal–carboxylate complexes with diverse structures have been
obtained. We focus our attention on study of inorganic–organic hy-
brids with carboxylate-containing ligands and have obtained vari-
ous metal complexes with interesting structures and properties in
recent years [13–17]. In this context, we have designed a bifunc-
tional carboxylic and pyridine-containing ligand, namely 4-(isoni-
cotinamido)phthalic acid (H2L), since the multicarboxylate ligands
containing N-donors are not well studied, except for the limited
examples such as pyridine-2,6-dicarboxylic acid, isonicotinic acid
and 5-(isonicotinamido)isophthalic acid [17]. The majority of this
research focuses on the synthesis, structural characterization and
properties of complexes constructed from different divalent metal
salts and H2L. In this paper, four new hybrids, namely
[Mn(L)(H2O)2]n (1), {[Co(L)(H2O)3]ꢀ2H2OꢀCH3OH}n (2), {[Zn(L)
(H2O)]ꢀH2O}n (3) and [Cd(HL)2]n (4), were prepared to investigate
optical property of 3 and photoluminescence of 3 and 4 were
investigated (Supplementary data).
2. Experimental
2.1. Materials and measurements
All commercially available solvents and starting materials were
used as received without further purification. FT-IR spectra were
recorded on a Bruker Vector22 FT-IR spectrophotometer using
KBr disks. Elemental analyses for C, H and N were taken on a Per-
kin–Elmer 240C elemental analyzer at the Analysis Center of Nan-
jing University. The magnetic susceptibilities in the temperature
range of 1.8–300 K were measured on a Quantum Design MPMS7
SQUID magnetometer in a field of 2000 Oe. Diamagnetic correc-
tions were made with Pascal’s constants for all samples. The
second-order nonlinear optical (NLO) intensity was estimated by
measuring a powder sample of 80–150
of a pellet relative to urea. A pulsed Q-switched Nd:YAG laser at
wavelength of 1064 nm was used to generate second-
lm diameter in the form
a
harmonic-generation (SHG) signal. The backscattered SHG light
was collected by a spherical concave mirror and passed through
a filter that transmits only 532 nm radiation. The luminescent
spectra for the solid powdered samples were recorded at room
* Corresponding author. Tel.: +86 25 8359 3485; fax: +86 25 8331 4502.
E-mail address: sunwy@nju.edu.cn (W.-Y. Sun).
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.05.014

M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
2455
temperature on an Aminco Bowman Series 2 spectrophotometer
with xenon arc lamp as the light source. In the measurements of
the emission and excitation spectra, the pass width was 5.0 nm.
All the measurements were carried out under the same conditions.
2.3.2. Synthesis of {[Co(L)(H2O)3]ꢀ2H2OꢀCH3OH}n (2)
A mixture of H2L (0.028 g, 0.10 mmol), Co(NO3)2ꢀ6H2O (0.030 g,
0.10 mmol), NaOH (0.008 g, 0.20 mmol), CH3OH (2 mL) and H2O
(6 mL) was sealed in a 15 mL Teflon liner autoclave at 140 °C for
three days. After cooling to room temperature, pink platelet crys-
tals of complex 2 were collected with a yield of 44%. Anal. Calc.
for C15H22CoN2O11 (2): C, 38.72; H, 4.77; N, 6.02. Found: C,
38.64; H, 4.81; N, 5.97%. IR (KBr pellet, cmꢁ1): 3425 (s), 1672 (s),
1618 (s), 1586 (s), 1534 (m), 1404 (m), 1384 (s), 797 (m), 709
(m), 665 (w), 621 (w).
2.2. Synthesis of the ligand 4-(isonicotinamido)phthalic acid (H2L)
Isonicotinoyl chloride hydrochloride (3.56 g, 20 mmol) was sus-
pended in tetrahydrofuran (40 mL), then triethylamine (4.0 mL)
and a solution of 4-aminophthalic acid (3.62 g, 20 mmol) in tetra-
hydrofuran (40 mL) were added. The mixture was stirred at room
temperature for 24 h, the resulting precipitate was filtered, washed
with hot water and ethanol, and dried in air to give the ligand
(3.6 g, 63%). IR (KBr, cmꢁ1): 3260 (s), 3107 (s), 1717 (m), 1681
(s), 1608 (s), 1532 (s), 1370 (s), 1326 (ms), 849 (m), 772 (s), 656
(ms). 1H NMR (500 MHz, DMSO-d6): d 9.06 (s, 2H), 8.74 (s, 1H),
8.32 (s, 1H), 8.20 (s, 1H), 8.04 (s, 1H), 7.94 (s, 2H).
2.3.3. Synthesis of {[Zn(L)(H2O)]ꢀH2O}n (3)
The preparation of 3 is similar to that of 1 except that
MnCl2ꢀ4H2O was replaced by Zn(NO3)2ꢀ6H2O (0.029 g, 0.10 mmol).
After cooling to room temperature, colorless platelet crystals of 3
were collected in 52% yield. Anal. Calc. for C14H12ZnN2O7 (3): C,
43.60; H, 3.14; N 7.26. Found: C, 43.63; H, 3.20; N, 7.21%. IR (KBr
Table 2
2.3. Synthesis of the complexes
Selected bond lengths (Å) and angles (°) for 1–4.
1a
2.3.1. Synthesis of [Mn(L)(H2O)2]n (1)
Mn(1)–O(1)
Mn(1)–O(1W)
Mn(1)–O(2W)
O(1)–Mn(1)–O(1W)
O(1)–Mn(1)–O(2W)
O(1)–Mn(1)–O(3)#2
O(1)–Mn(1)–N(2)#3
O(1W)–Mn(1)–O(2)#1
O(1W)–Mn(1)–O(3)#2
2.192(2)
2.109(2)
2.156(2)
91.80(7)
90.77(6)
84.47(6)
91.22(6)
89.14(6)
97.88(6)
Mn(1)–O(2)#1
Mn(1)–O(3)#2
Mn(1)–N(2)#3
O(1W)–Mn(1)–N(2)#3
O(2)#1–Mn(1)–O(2W)
O(2W)–Mn(1)–O(3)#2
O(2W)–Mn(1)–N(2)#3
O(2)#1–Mn(1)–O(3)#2
O(2)#1–Mn(1)–N(2)#3
2.178(2)
2.171(1)
2.324(2)
87.54(6)
88.91(6)
88.80(6)
85.96(6)
90.16(6)
94.11(6)
A mixture of H2L (0.028 g, 0.10 mmol), MnCl2ꢀ4H2O (0.020 g,
0.10 mmol), NaOH (0.008 g, 0.20 mmol), H2O (8 mL) was kept in
a 15 mL Teflon liner autoclave at 140 °C for three days. After the
reaction mixture was cooled to room temperature, brown block
crystals of complex 1 were collected with a yield of 64%. Anal. Calc.
for C14H12MnN2O7 (1): C, 44.82; H, 3.22; N, 7.47. Found: C, 44.78;
H, 3.29; N, 7.51%. IR (KBr pellet, cmꢁ1): 3421 (s), 1653 (s), 1618
(m), 1580 (s), 1540 (w), 1524 (s), 1407 (m), 1354 (m), 1318 (m),
840 (m), 799 (m), 699 (w), 671 (w), 599 (w).
2b
Co(1)–O(1)
Co(1)–O(1W)
Co(1)–O(2W)
O(1)–Co(1)–O(1W)
O(1)–Co(1)–O(2W)
O(1)–Co(1)–O(3W)
O(1)–Co(1)–N(1)#1
O(1)–Co(1)–O(3)#2
O(1W)–Co(1)–O(2W)
O(1W)–Co(1)–N(1)#1
2.176(3)
2.087(3)
2.099(3)
90.2(1)
169.3(1)
85.6(1)
84.8(1)
99.9(1)
96.6(1)
91.3(1)
Co(1)–O(3W)
Co(1)–N(1)#1
Co(1)–O(3)#2
O(1W)–Co(1)–O(3)#2
O(2W)–Co(1)–O(3W)
O(2W)–Co(1)–N(1)#1
O(2W)–Co(1)–O(3)#2
O(3W)–Co(1)–N(1)#1
O(3)#2–Co(1)–O(3W)
2.103(3)
2.132(4)
2.080(3)
84.3(1)
88.6(1)
86.8(1)
89.0(1)
95.2(1)
89.6(1)
Table 1
Crystallographic data for 1–4.
Complex
1
2
3
4
Formula
Formula
weight
Crystal
system
C
14H12MnN2O7 C15H22CoN2O11 C14H12ZnN2O7 C28H18CdN4O10
375.20
465.20
385.63
682.86
monoclinic
monoclinic
orthorhombic monoclinic
3c
Zn(1)–O(2)
1.970(3)
1.945(3)
112.6(1)
112.8(2)
99.1(1)
Zn(1)–N(11)
Zn(1)–O(41)#2
O(2)–Zn(1)–O(31)#1
O(31)#1-Zn(1)–N(11)
O(31)#1–Zn(1)–O(41)#2
2.034(3)
1.924(3)
100.9(1)
109.1(1)
122.7(2)
Space group P21/n
C2/c
Pca21
24.636(8)
7.932(3)
7.200(2)
90.00
90.00
90.00
1407.1(9)
4
P21/n
Zn(1)–O(31)#1
O(2)–Zn(1)–N(11)
O(2)–Zn(1)–O(41)#2
O(41)#2–Zn(1)–N(11)
a (Å)
b (Å)
c (Å)
6.4311(7)
21.764(3)
7.3700(11)
24.119(4)
90.00
95.197(3)
90.00
9.1382(10)
11.8973(13)
22.921(3)
90.00
92.059(2)
90.00
30.353(3)
7.2962(8)
90.00
a
(°)
b (°)
92.134(2)
90.00
1423.3(3)
4
4d
c
(°)
Cd(1)–O(1)
Cd(1)–N(4)
Cd(1)–O(2)#2
Cd(1)–O(7)#3
2.304(3)
2.277(3)
2.398(3)
2.306(2)
52.92(9)
81.74(9)
102.7(1)
141.34(8)
88.65(9)
90.0(1)
130.57(9)
54.30(8)
84.72(9)
139.0(1)
92.06(9)
Cd(1)–O(2)
Cd(1)–N(2)#1
Cd(1)–O(6)#3
2.579(3)
2.358(3)
2.513(3)
V (Å3)
Z
3852.8(10)
8
2490.4(5)
4
T (K)
293(2)
0.971
293(2)
0.952
1.570
1848
9299
200
293(2)
0.950
1.821
1368
12390
l
(mmꢁ1
)
1.790
1.820
784
O(1)–Cd(1)–O(2)
O(7)#3–Cd(1)–N(2)#1
O(1)–Cd(1)–N(4)
O(2)#2–Cd(1)–O(6)#3
O(2)#2–Cd(1)–O(7)#3
O(1)–Cd(1)–N(2)#1
O(1)–Cd(1)–O(2)#2
O(6)#3–Cd(1)–O(7)#3
O(1)–Cd(1)–O(6)#3
O(1)–Cd(1)–O(7)#3
O(2)–Cd(1)–N(4)
O(2)–Cd(1)–N(2)#1
O(2)–Cd(1)–O(2)#2
O(2)–Cd(1)–O(6)#3
O(2)–Cd(1)–O(7)#3
N(2)#1–Cd(1)–N(4)
O(2)#2–Cd(1)–N(4)
O(6)#3–Cd(1)–N(4)
O(7)#3–Cd(1)–N(4)
O(2)#2–Cd(1)-N(2)#1
O(6)#3–Cd(1)–N(2)#1
94.79(9)
78.70(9)
137.50(8)
167.2(1)
167.2(1)
86.9(1)
101.6(1)
89.23(9)
83.9(1)
Dcalc (g/m3) 1.751
F(0 0 0)
Reflections
collected
Unique
4488
764
7384
12773
reflections 2639
3396
1.037
3174
0.992
Goodness-of- 0.940
fit (GOF)
1.070
on F2
80.4(1)
Rint
0.0776
(I)] 0.0394
0.0971
0.0596
0.1503b
0.0584
0.0403
0.0935c
0.0500
0.0398
0.0651d
R1[I > 2
r
a
wR2[I > 2r
(I)] 0.1037a
Symmetry transformations used to generate equivalent atoms: #1: 1 + x, y, z,
ꢁz + 1/2, #2: 1 ꢁ x, 1 ꢁ y, ꢁz, #3: 1/2 + x, 1/2 ꢁ y, ꢁ1/2 + z.
Residues
ꢁ0.565, 0.586 ꢁ0.529, 0.838 ꢁ0.667, 0.461 ꢁ0.427,
b
(e Åꢁ3
)
0.819
Symmetry transformations used to generate equivalent atoms: #1: x + 1/2,
ꢁy + 3/2, z + 1/2, #2: ꢁx + 3/2, y + 1/2, ꢁz + 3/2.
2
2
a
b
c
c
w ¼ 1=½r2ðF0Þ þ ð0:1685PÞ þ 0:1685Pꢂ;
where P ¼ ðF20 þ 2Fc2Þ=3.
Symmetry transformations used to generate equivalent atoms: #1: 1 ꢁ x, 1 ꢁ y,
2
2
w ¼ 1=½r2ðF0Þ þ ð0:0728PÞ ꢂ;
where P ¼ ðF20 þ 2Fc2Þ=3.
ꢁ1/2 + z, #2: ꢁ1/2 + x, 1 ꢁ y, z.
2
2
w ¼ 1=½r2ðF0Þ þ ð0:0490PÞ þ 1:4963Pꢂ; where P ¼ ðF02 þ 2F2c Þ=3.
w ¼ 1=½r2ðF0Þ2 þ ð0:0150PÞ2ꢂ; where P ¼ ðF02 þ 2F2c Þ=3.
Symmetry transformations used to generate equivalent atoms: #1: 1/2 ꢁ x, ꢁ1/
d
d
2 + y, 5/2 ꢁ z, #2: 1 ꢁ x, 1 ꢁ y, 2 ꢁ z, #3: ꢁ1/2 + x, 1/2 ꢁ y, 1/2 + z.

2456
M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
pellet, cmꢁ1): 3424 (s), 1678 (s), 1611 (m), 1556 (m), 1528 (m),
1499 (w), 1425 (m), 1384 (s), 1324 (m), 1068 (m), 790 (m), 694
(w), 674 (w), 585 (w).
2.3.4. Synthesis of [Cd(HL)2]n (4)
The title complex was prepared by layering method. An aque-
ous solution (5 mL) of H2L (0.028 g, 0.10 mmol) was carefully ad-
(a)
(b)
(c)
Fig. 1. (a) Coordination environment of Mn(II) atom in 1 with the ellipsoids drawn at the 30% probability level, hydrogen atoms were omitted for clarity. (b) 3D framework of
the polymer that possesses a 1D rectangular channel along c-axis. (c) The extended framework topology of 1 is congruent with that of sra.

M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
2457
justed to pH 6 by using tetrabutylammonium hydroxide (10%)
solution and placed at the bottom of a test tube. Then a buffer layer
of a solution (5 mL) of methanol/H2O (1:1) was layered over it, and
afterward, a solution of Cd(NO3)2ꢀ4H2O (0.031 g, 0.10 mmol) in
methanol (5 mL) was layered over the buffer layer. Colorless block
crystals of 4 were collected in 38% yield after 20 days. Anal. Calc. for
In order to better identify the nature of the structure of complex
1, suitable connectors can be defined by using the topological ap-
proach [23–25]. As discussed above, each L2ꢁ ligand is neighbored
by four Mn(II) atoms, and thus can be considered as a four-connec-
tor. Meanwhile, the central Mn(II) atom can also be viewed as a
four-connector by omitting the coordination of two terminal water
molecules. Analysis of the vertex symbols and coordination se-
quence of 1 revealed that its topology is related to SrAl2 (sra) with
Schläfli symbol of (42ꢀ63ꢀ8) as depicted in Fig. 1c. Namely a net has
been referred by Smith as the ABW tetrahedral net in Li-ABW zeo-
lite while O’Keeffe and Hyde refer it as the sra net [26–29].
C28H18CdN4O10 (4): C, 49.25; H, 2.66%; N, 8.20. Found: C, 49.21; H,
2.70; N, 8.17%. IR (KBr pellet, cmꢁ1): 3425 (s), 1699 (s), 1673 (s),
1616 (vs), 1584 (vs), 1535 (m), 1404 (m), 1382 (s), 797 (m), 710
(m), 667 (w), 624 (w).
2.4. Crystal structure determination
3.1.2. {[Co(L)(H2O)3]ꢀ2H2OꢀCH3OH}n (2)
Crystallographic data of 1, 2 and 4 were collected at 293 K on a
When the H2L ligand was used to react with Co(NO3)2ꢀ6H2O,
NaOH at 140 °C for three days, complex 2 was isolated. The struc-
ture of 2 was studied by X-ray single-crystal structure determina-
tion. The asymmetric unit of 2 consists of one Co(II) atom, one L2ꢁ
ligand, three coordinated and two free water molecules, and one
uncoordinated methanol molecule. The coordination environment
of Co(II) atom in 2 is shown in Fig. 2a with atom numbering
scheme. Each Co(II) atom is coordinated by one pyridyl nitrogen
(N1B) and two carboxylate oxygen (O1, O3A) atoms from three dis-
tinct L2ꢁ ligands and three oxygen atoms (O1W, O2W, O3W) from
three water molecules, respectively. The bond angles around the
Co(II) atom are in the range of 84.33(12)–173.55(13)° (Table 2),
and thus the coordination geometry of the Co(II) atom is distorted
octahedral with NO5 donor set. The Co1–N bond length is
2.132(4) Å and the Co1–O ones are in the range from 2.080(3) to
2.176(3) Å (Table 2). On the other hand, each L2ꢁ ligand in 2 uses
Bruker SMART CCD system equipped with graphite-monochromat-
ed Mo K
a
radiation (k = 0.71073 Å) using
x
ꢁ u scan technique.
The data integration and empirical absorption corrections were
carried out by SAINT programs [18]. The structures were solved by
direct methods (SHELXS 97) [19]. All the non-hydrogen atoms were
refined anisotropically on F2 by full-matrix least-squares tech-
niques (SHELXL 97) [20]. All the hydrogen atoms except for those
of water molecules were generated geometrically and refined iso-
tropically using the riding model, while those of water molecules
in 1 were found directly. Crystallographic data collection for com-
plex 3 was carried out on a Rigaku RAXIS-RAPID Imaging Plate dif-
fractometer at 200 K, using graphite-monochromated Mo
Ka
radiation (k = 0.71075 Å). The structure of 3 was solved by direct
methods with SIR92 [21] and expanded using Fourier techniques
[22]. All the non-hydrogen atoms were refined anisotropically on
F2 by full-matrix least-squares methods. All the hydrogen atoms
of ligands in 3 were generated geometrically. Details of the crystal
parameters, data collection and refinements for 1–4 are summa-
rized in Table 1. Selected bond lengths and angles for 1–4 are listed
in Table 2.
M
M
N
N
3. Results and discussion
O
NH
3.1. Crystal structures of complexes 1–4
O
NH
3.1.1. [Mn(L)(H2O)2]n (1)
O
The result of X-ray crystallographic analysis revealed that com-
plex 1 crystallizes in monoclinic space group P21/n (Table 1). As
shown in Fig. 1a, each Mn(II) atom is six-coordinated with dis-
torted octahedral coordination geometry by one pyridyl nitrogen
(N2A) and three carboxylate oxygen (O1, O2B, O3C) atoms from
four different L2ꢁ ligands, and two oxygen (O1W, O2W) atoms
from two terminal coordinated water molecules. The Mn1–O bond
distances in 1 range from 2.1086(16) to 2.1924(16) Å, and the
Mn1–N one is 2.324(2) Å, and the coordination angles around
Mn(II) vary from 84.47(6) to 174.62(6)° as listed in Table 2. It is
noteworthy that the two carboxylate groups of each L2ꢁ ligand
connect three Mn(II) atoms with different coordination modes of
O
O
O
O
M
O
M
M
M
O
O
M
(a)
(b)
M
M
N
N
l1- :g - :g
g1 0 monodentate and l2 g1 1 bis-monodentate, respectively,
in addition the pyridyl group of each L2- coordinates with one
Mn(II) (Scheme 1a). Therefore, the coordination interactions be-
tween the four-connecting L2ꢁ ligand and six-coordinated Mn(II)
atom as described above make 1 a three-dimensional (3D) frame-
O
NH
O
NH
OH
OH
work. Firstly, one-dimensional (1D) [Mn(OCO)] double chain is
1
formed by the connections between the carboxylate groups of
L2ꢁ and Mn(II) atoms if the coordination of pyridyl group with
Mn(II) is neglected (Fig. 1b). The inter- and intra-chain Mn–Mn dis-
tances of Mn1–Mn1A and Mn1–Mn1B (Fig. 1b) are 5.20 Å and
6.43 Å, respectively. Then, the 1D chains are cross-linked by pyri-
dyl groups of L2ꢁ, leading to the formation of 3D extended frame-
work of 1 with 1D rectangular channels (Fig. 1b).
O
O
O
O
O
O
M
M
M
(c)
(d)
Scheme 1. Coordination modes of H2L ligand in complexes 1–4.

2458
M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
its pyridyl and two carboxylate groups to connect three Co(II)
atoms. Different from those in complex 1, the two carboxylate
groups of each L2ꢁ ligand in 2 have the same coordination mode
one aqua ligand (O2) (Fig. 3a), with Zn–O bond distances ranging
from 1.924 (3) to 1.970(3) Å and Zn1–N bond length of
2.034(3) Å (Table 2). Each L2ꢁ ligand acts as a three-connector to
link three Zn(II) atoms in complex 3 (Scheme 1b), which is similar
of l1- :g
g1 0- monodentate (Scheme 1b).
In complex 2, the Co(II) atoms are linked together by the car-
boxylate groups of L2ꢁ to form an infinite 1D zigzag chain if the
Co–N connections are neglected, which is further linked together
through the Co–N coordination leading to the formation of a
two-dimensional (2D) network (Fig. 2b). As described above, each
Co(II) is surrounded by three L2ꢁ ligands and each L2ꢁ ligand links
three Co(II) atoms. Thus, both Co(II) atom and L2ꢁ ligand can be
considered as three-connected nodes in a ratio of 1:1 in 2.
Therefore, the complex 2 exhibits a (3,3)-connected 2D network
with (4,82) topology as clearly shown in Fig. 2c. Furthermore, as
depicted in Fig. 2d, the 2D layers packed together through N–
Hꢀ ꢀ ꢀO, O–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀO hydrogen bonding interactions to give
a 3D framework. The hydrogen bonding data are summarized in
Table S1.
to that in 2, namely each carboxylate group displays l1- : -
g1 g0
monodentate mode and two carboxylate groups connect two Zn(II)
atoms, the pyridyl nitrogen atom binds to another Zn(II) atom, con-
sequently resulting in formation of a 2D layer structure (Fig. 3b).
Similar topological method was used to get insight of the struc-
ture of 3. As discussed above, both each Zn(II) and L2ꢁ ligand can be
defined as three-connecting nodes since they connect three L2ꢁ li-
gands and three metal ions, respectively, then a 2D network with
(6,3) topology is yielded as illustrated in Fig. 3c, which is different
from those in complexes 1 and 2. Furthermore, the most striking
feature of 3 is that the 2D (6,3) networks are connected together
through the N–Hꢀ ꢀ ꢀO together with C–Hꢀ ꢀ ꢀO hydrogen-bonding
interactions (Table S1) to produce a 3D framework (Fig. S1) with
hms topology and Schläfli symbol of (63)(69ꢀ8) by taking the N1–
H1ꢀ ꢀ ꢀO32 hydrogen-bonding interaction into account (Fig. 3d)
[30]. The different structures of complexes 1–3 showed that the
metal ions play crucial role in determining the structure of the
frameworks.
3.1.3. {[Zn(L)(H2O)]ꢀH2O}n (3)
When Zn(NO3)2ꢀ6H2O, instead of MnCl2ꢀ4H2O used in prepara-
tion of 1, was used to react with ligand H2L, complex 3 with a 2D
layer structure was obtained. The results of X-ray crystallographic
analysis indicate that the Zn(II) atom in 3 has distorted tetrahedral
coordination geometry with two oxygen (O31A, O41B) atoms and
one nitrogen (N11) atom from three separated L2ꢁ ligands and
3.1.4. [Cd(HL)2]n (4)
When the reaction of ligand H2L with Cd(NO3)2ꢀ4H2O was car-
ried out by layering method, rather than the hydrothermal reaction
(b)
(a)
(c)
(d)
Fig. 2. (a) Coordination environment of Co(II) in 2 with the ellipsoids drawn at the 30% probability level, hydrogen atoms and guest molecules were omitted for clarity. (b)
Polyhedral representation of the 2D layer structure in 2. (c) A uninodal 3-connected 2D (4,82) network of complex 2. (d) 3D packing structure of 2 with hydrogen bonds
indicated by the dashed lines.

M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
2459
used for preparation of 1–3, a new compound 4 was obtained. The
crystallographic data showed that complex 4 crystallizes in mono-
clinic P21/n space group and the Cd(II) atom has a pentagonal
bipyramid coordination geometry with a N2O5 donor set (Fig. 4a).
It should be noticed that in contrast to the complete deprotonation
of H2L to give L2ꢁ in 1–3, the H2L is only partial deprotonated to
generate HLꢁ in 4 as confirmed by crystallographic and IR spectral
data (a strong IR band from –COOH appeared at 1699 cmꢁ1, see
Section 2). As shown in Scheme 1c and d, the carboxylate groups
of two different HLꢁ ligands in 4 have different coordination modes
two- and three-connecting HL- ligands and seven-coordinated
Cd(II) atom as described above make 4 a 2D network with Cd2O2
rhombic subunit as depicted in Fig. 4b. The 2D networks are fur-
ther connected together by N–Hꢀ ꢀ ꢀO and C–Hꢀ ꢀ ꢀO hydrogen bonds
to give a 3D framework (Fig. S2, Table S1).
3.2. Properties
3.2.1. Magnetic property
As described above, the Mn(II) atoms are bridged by l2- :
g1 g1
of l2
connect one Cd(II). Such coordination interactions between the
- : - :
g1 g2 bridging to link two Cd(II) and l1 g1 g1 chelating to
bis-monodentate carboxylate groups to give [Mn(OCO)] chain
1
in 1 (Fig. 1b), and magnetic interactions may exist between the
(a)
(b)
(c)
(d)
Fig. 3. (a) Coordination environment of Zn(II) in 3 with the ellipsoids drawn at the 30% probability level, hydrogen atoms and water molecules were omitted for clarity. (b)
Polyhedral representation of the 2D layer structure in 3. (c) A uninodal 3-connected 2D (6,3) network of complex 3. (d) 3D hms net of 3 linked by hydrogen bonding shown by
dashed line.

2460
M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
Mn(II) atoms. Therefore, the temperature dependence of magnetic
susceptibilities of 1 was measured in the range of 300–1.8 K with
an applied magnetic field of 2000 Oe. As depicted in Fig. S3, the
advantages over pure organic or inorganic compounds, new NLO
made up by organic-inorganic hybrid coordination polymers are
especially interested [36,37]. Complex 3 crystallizes in acentric
space group Pca21, thus quasi-Kurtz second-harmonic-generation
(SHG) measurements were performed on powder sample of 3 to
confirm its acentricity as well as to evaluate its potential applica-
tion as second-order NLO material [38]. The preliminary result
showed the bulk materials of 3 display modest powder SHG activ-
ity with a response of approximately 0.5 times of that for urea.
v
MT value is 4.23 emu K molꢁ1 at room temperature, which is close
to the value of 4.37 emu K molꢁ1 expected for one magnetically
independent Mn(II) (S = 5/2) center. The MT decreases steadily
v
with decreasing temperature and reaches a value of 0.62 emu
K molꢁ1 at 1.8 K, indicating an overall antiferromagnetic behavior
between the Mn(II) ions. According to the structural data, such
magnetic behavior indicates the antiferromagnetic coupling within
the [Mn(OCO)] chain unit in 1 while the inter-chain interactions
1
and the coupling through the pyridyl groups of L2ꢁ are negligible.
Therefore, the magnetic interaction can be fitted to the isotropic
3.2.3. Luminescent properties
In general, fluorescence properties of inorganic–organic hybrid
coordination complexes, especially with d10 metal centers, have
been investigated owing to their potential applications as photoac-
tive materials [39–41]. In this study, the photoluminescence prop-
erties of 3 and 4 as well as Na2L were investigated in the solid state
at room temperature and the results are shown in Fig. S4. Intense
emissions were observed at 452 nm (kex = 360 nm) for Na2L,
465 nm (kex = 360 nm) for 3, 466 nm (kex = 360 nm) for 4, respec-
tively. Such emissions can be attributed to neither metal-to-ligand
charge transfer (MLCT) nor ligand-to-metal charge transfer (LMCT)
because the Zn(II)/Cd(II) ions are in d10 configuration and difficult
to oxidize or to reduce. Therefore the emissions observed in 3 and
Hamiltonian H = ꢁ2J
RSiSi+1, and the analytical expression derived
by Fisher for the 1D Heisenberg chain of classical spins (S = 5/2)
was used [31–35]. The results revealed that the best least-square
fit of the theoretical equation to experimental data gave g = 2.03,
J = ꢁ0.54 cmꢁ1
,
TIP = 0.0008 cmꢁ1 and the agreement factor
v
P
P
R = [(
v
MT)obsd ꢁ (
MT)calcd]2/
(v
MT)2
is 1.0 ꢃ 10ꢁ5. The neg-
obsd
ative J value further confirms the existence of antiferromagnetic
interactions in 1.
3.2.2. Nonlinear optical property of 3
*
p–p intrali-
It is known that a non-centrosymmetric structure may have
second-order non-linear optical (NLO) effects, and due to the
4 are tentatively considered to be attributed to the
gand photoluminescence due to their resemblance to that of
(a)
(b)
Fig. 4. (a) Coordination environment of Cd(II) in 4 with the ellipsoids drawn at the 30% probability level, hydrogen atoms were omitted for clarity. (b) Polyhedral
representation of the 2D layer structure in 4.

M.-S. Chen et al. / Polyhedron 29 (2010) 2454–2461
2461
[10] L. Pan, H.M. Liu, X.G. Lei, X.Y. Huang, D.H. Olson, N.J. Turro, J. Li, Angew. Chem.,
Int. Ed. 42 (2003) 542.
[11] X.L. Wang, C. Qin, E.B. Wang, Y.G. Li, C.W. Hu, L. Xu, Chem. Commun. (2004)
Na2L ligand, and the slight red-shifts of 3 and 4 compared to that of
Na2L probably result from the fact that the coordination of L to
Zn(II)/Cd(II) increases the ligand conformational rigidity and thus
reduces the non-radiative energy loss [42–44].
378.
[12] S. Kitagawa, R. Kitaura, S.-i. Noro, Angew. Chem., Int. Ed. 43 (2004) 2334.
[13] J. Xu, Z.S. Bai, T.-a. Okamura, M.S. Chen, W.Y. Sun, N. Ueyama, Polyhedron 28
(2009) 2480.
4. Conclusions
[14] Q. Chu, G.X. Liu, T.-a. Okamura, Y.Q. Huang, W.Y. Sun, N. Ueyama, Polyhedron
27 (2008) 812.
[15] Z.S. Bai, Z.P. Qi, Y. Lu, Q. Yuan, W.Y. Sun, Cryst. Growth Des. 8 (2008) 1924.
[16] Z.S. Bai, J. Xu, T.-a. Okamura, M.S. Chen, W.Y. Sun, N. Ueyama, Dalton Trans.
In summary, we have successfully synthesized four new hybrids
based on a new pyridine- and carboxylate-containing ligand 4-
(isonicotinamido)phthalic acid with corresponding metal salts.
The results revealed that it is promising to build up specific struc-
tures via combining transition metals and pyridyl-carboxylate li-
gands. The varied coordination modes of the ligand found in the
present work prove that it is a useful building block in the prepa-
ration of novel hybrid frameworks with potential magnetic and
luminescent properties.
(2009) 2528.
[17] M.S. Chen, Z.S. Bai, Z. Su, S.S. Chen, W.Y. Sun, Inorg. Chem. Commun. 12 (2009)
530.
[18] SAINT, Program for Data Extraction and Reduction, Bruker AXS, Inc., Madison,
WI, 2001.
[19] G.M. Sheldrick,
University of Göttingen, Germany, 1997.
[20] G.M. Sheldrick, HELXL-97, Program for Refinement of Crystal Structures,
SHELXS-97, Program for the Solution of Crystal Structures,
S
University of Göttingen, Germany, 1997.
[21] SIR92: A. Altomare, M.C. Burla, M. Camalli, M. Cascarano, C. Giacovazzo, A.
Guagliardi, G. Polidori, J. Appl. Crystallogr. 27 (1994) 435.
[22] DIRFID 94: P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, R. de
Gelder, R. Israel, J.M.M. Smits, The DIRFID-94 Program System; Technical
Report of the Crystallography Laboratory, University of Nijmegen, Nijmegen,
The Netherlands, 1994.
[23] N.W. Ockwig, O. Delgado-Friederichs, M. O’Keeffe, O.M. Yaghi, Acc. Chem. Res.
38 (2005) 176.
[24] O.M. Yaghi, H. Li, C. Davis, D. Richardson, T.L. Groy, Acc. Chem. Res. 31 (1998)
474.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (Grant Nos. 20731004 and
20721002) and the National Basic Research Program of China
(Grant Nos. 2007CB925103 and 2010CB923303).
[25] S.R. Batten, R. Robson, Angew. Chem., Int. Ed. 37 (1998) 1460.
[26] K.E. Holmes, P.F. Kelly, M.R.J. Elsegood, Dalton Trans. (2004) 3488.
[27] P.S. Wang, C.N. Moorefield, M. Panzer, G.R. NewKome, Chem. Commun. (2005)
465.
Appendix A. Supplementary data
[28] M. O’Keeffe, M. Eddaoudi, H.L. Li, T. Reineke, O.M. Yaghi, J. Solid State Chem.
152 (2000) 3.
CCDC 760534, 760535, 760536, and 7605347 contain the sup-
plementary crystallographic data for 1, 2, 3 and 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 Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223 336
033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data asso-
ciated with this article can be found, in the online version, at
doi:10.1016/j.poly.2010.05.014.
[29] N.L. Rosi, M. Eddaoudi, J. Kim, M. O’Keeffe, O.M. Yaghi, Angew. Chem., Int. Ed.
41 (2002) 284.
}
[30] O.V. Dolomanov, A.J. Blake, N.R. Charmpness, M. Schroder, J. Appl. Crystallogr.
36 (2003) 1283.
[31] M.E. Fisher, Am. J. Phys. (Paris) 32 (1964) 343.
[32] C.J. O’Connor, Prog. Inorg. Chem. 29 (1982) 203.
[33] R.H. Wang, D.Q. Yuan, F.L. Jiang, L. Han, S. Gao, M.C. Hong, Eur. J. Inorg. Chem.
(2006) 1649.
[34] J. Li, S.B. Tang, L. Lu, H.C. Zeng, J. Am. Chem. Soc. 129 (2007) 9401.
[35] W. Chen, Q. Yue, C. Chen, H.M. Yuan, W. Xu, J.S. Chen, S.N. Wang, Dalton Trans.
(2003) 28.
[36] H.S. Ra, K.M. Ok, P.S. Halasyamani, J. Am. Chem. Soc. 125 (2003) 7764.
[37] J.S.O. Evans, S. Bénard, P. Yu, R. Clément, Chem. Mater. 13 (2001) 3813.
[38] L. Song, S.W. Du, J.D. Lin, H. Zhou, T. Li, Cryst. Growth Des. 7 (2007) 2268.
[39] A. Vogler, H. Kunkely, Coord. Chem. Rev. 250 (2006) 1622.
[40] R.Q. Fan, D.S. Zhu, Y. Mu, G.H. Li, Y.L. Yang, Q. Su, S.H. Feng, Eur. J. Inorg. Chem.
(2004) 4891.
[41] L.L. Wen, Y.Z. Li, Z.D. Lu, J.G. Lin, C.Y. Duan, Q.J. Meng, Cryst. Growth Des. 6
(2006) 530.
[42] U.H.F. Bunz, Chem. Rev. 100 (2000) 1605.
[43] W.Y. Yang, H. Schmider, Q.G. Wu, Y.S. Zhang, S.N. Wang, Inorg. Chem. 39
(2000) 2397.
[44] Y.B. Chen, J. Zhang, J.K. Cheng, Y. Kang, Z.J. Li, Y.G. Yao, Inorg. Chem. Commun. 7
(2004) 1139.
References
´
[1] J. Mrozinski, Coord. Chem. Rev. 249 (2005) 2534.
[2] J.L. Atwood, Nat. Mater. 1 (2002) 91.
[3] M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O.M. Yaghi,
Science 295 (2002) 469.
[4] R.Q. Zou, H. Sakurai, S. Han, R.Q. Zhong, Q. Xu, J. Am. Chem. Soc. 129 (2007)
8402.
[5] X.J. Kong, Y.P. Ren, L.S. Long, Z.P. Zheng, R.B. Huang, L.S. Zheng, J. Am. Chem.
Soc. 129 (2007) 7016.
[6] N. Guillou, C. Livage, W. van Beek, M. Noguès, G. Férey, Angew. Chem., Int. Ed.
42 (2003) 643.
[7] S. Ghosh, P.S. Mukherjee, Dalton Trans. (2007) 2542.
[8] M. Dan, C.N.R. Rao, Angew. Chem., Int. Ed. 45 (2006) 281.
[9] A.Y. Robin, K.M. Fromm, Coord. Chem. Rev. 250 (2006) 2127.