Synthesis, structures and properties of four coordination polymers constructed from 5-nitroisophthalate and benzimidazole ligand

Article abstract of DOI:10.1002/zaac.200700327

Four coordination polymers, [Cu(NIPH)(Bim)₂]_n (1), [Co(NIPH)(Bim)₂]_n (2), [Zn(NIPH)(Bim)]_n (3), and [Cd(NIPH)(Bim)(H₂O)]_n (4) (NIPH = 5-nitroisophthalate and Bim = benzimidazole)

Full text of DOI:10.1002/zaac.200700327

DOI: 10.1002/zaac.200700327
Synthesis, Structures and Properties of Four Coordination Polymers
Constructed from 5-Nitroisophthalate and Benzimidazole Ligand
Jun-Wei Ye, Di Li, Kai-Qi Ye, Yu Liu, Yun-Feng Zhao, and Ping Zhang*
Changchun / China, Key Laboratory for Supramolecular Structure and Materials of Ministry of Education, College of Chemistry, Jilin
University
Received May 16th, 2007.
Abstract. Four coordination polymers, [Cu(NIPH)(Bim)2]n
(1), [Co(NIPH)(Bim)2]n (2), [Zn(NIPH)(Bim)]n (3), and
[Cd(NIPH)(Bim)(H2O)]n (4) (NIPH ϭ 5-nitroisophthalate and
Bim ϭ benzimidazole) have been synthesized and characterized by
elemental analysis, IR, TGA and single-crystal X-ray diffraction.
The crystal structural analyses reveal that 1 and 2 are composed of
zig-zag chains and straight line chains, respectively. 3 and 4 are
constructed by double-stranded loop-like chains. All these chain-
like structures are finally packed into three-dimensional networks
through hydrogen bonds. Thermogravimetic analyses (TGA) of
1Ϫ4 and temperature-dependent magnetic susceptibilities of 1 have
been performed.
Keywords: Coordination polymers; Crystal structure; Chain struc-
tures; Hydrogen bond
Introduction
of the coordination polymers [16Ϫ18]. In this contribution,
we report the syntheses and structures of four coordination
polymers [Cu(NIPH)(Bim)2]n (1), [Co(NIPH)(Bim)2]n (2),
[Zn(NIPH)(Bim)]n (3), and [Cd(NIPH)(Bim)(H2O)]n (4)
based on NIPH as bridging ligand and benzimidazole
(Bim) as terminal ligand. Thermogravimentric and mag-
netic properties of the coordination polymers are presented.
In last decade, the rational design and construction of coor-
dination polymers have attracted great attentions [1Ϫ6].
Particularly, metal carboxylate based coordination poly-
mers, as a new class of functional materials, have been
widely explored because of their interesting molecular top-
ologies and potential applications such as absorption, selec-
tive catalysis, optoelectronic and magnetic materials [7Ϫ8].
As an important family of carboxylate ligands, aromatic di-
carboxylate ligands, 1,3-benzendicarboxylate (1,3-BDC),
1,4-benzendicarboxylate (1,4-BDC) and 4,4Ј-biphenyldicar-
boxylate (BPDC), have been used widely in the construc-
tions of robust coordination frameworks with or without
Experimental Section
Materials and methods
5-Nitroisophthalic acid (H2NIPH) and benzimidazole (Bim) were
purchased from Fluka and used without further purification. All
of other reagents were procured from commercial sources and used
as received. Elemental analysis was performed on a Perkin-Elmer
2400 CHN Elemental Analyzer. Thermogravimetric analysis
(TGA) was carried out on a Perkin-Elmer TGA 7 unit with a heat-
ing rate of 10 °C/min in air. IR spectra were measured on a Nicolet
´
auxiliary ligands [9Ϫ11]. Yaghi [1a, 12], Ferey [13], Rao [7a,
14] and their co-workers have pursued the assembly of
MOFs with extended structures and novel adsorption and
magnetic properties based on these ligands. Furthermore,
the derivatives of dicarboxylate ligands containing func-
tional groups such as amine, hydroxyl, sulfonate and nitryl
groups have also been used to construct new supramolecu-
lar compounds [7a, 15]. For example, recent studies have
demonstrted that 5-nitroisophthalate (NIPH) is a multi-
functional ligand containing both carboxylate and nitryl
groups, which can potentially afford various coordination
modes and act as hydrogen-bond acceptors in the formation
5PC FT-IR spectrophotometer in the range of 4000-400 cmϪ1
.
Magnetic susceptibility data were collected over the temperature
range 2-300 K at a magnetic field of 2000 Oe on a Quantum Design
MPMS-7 SQUID magnetometer.
Preparation of [Cu(NIPH)(Bim)2]n (1)
A mixture of Cu(CH3COO)2 ·H2O (0.100 g, 0.5 mmol), H2NIPH
(0.106 g, 0.5 mmol)), Bim (0.120 g, 1 mmol), and H2O (10 mL) was
stirred for 30 min and heated at 120 °C for 72 hours in a Teflon-
lined stainless steel autoclave (25 mL) under autogenous pressure.
After cooling to room temperature, block-shaped crystals were ob-
tained with yield of 70 % based on Cu. Element analysis calcd for
C22H15N5O6Cu: C 51.92; H 2.97; N 13.76 %; Found: C 51.75; H
2.61; N 13.98 %. IR (KBr, cmϪ1) data: 3097(w), 1627(vs), 1564(m),
* Prof. P. Zhang
Key Laboratory for Supramolecular Structure and Materials of
Ministry of Education, College of Chemistry, Jilin University
Changchun 130012/P.R. China
Fax: ϩ86-431-85168439
E-mail: zhangping@jlu.edu.cn
Z. Anorg. Allg. Chem. 2008, 634, 345Ϫ351
 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
345

J.-W. Ye, D. Li, K.-Q. Ye, Y. Liu, Y.-F. Zhao, P. Zhang
1530(s), 1499(m), 1454(w), 1346(s), 1304(w), 1245(m), 1197(w),
1102(w), 1011(m), 982(m), 887(m), 770(m), 735(s), 614(w).
1558(s), 1533(s), 1453(m), 1380(w), 1344(w), 1248(w), 1189(w),
1081(w), 922(m), 788(w), 735(vs), 600(w).
Preparation of [Co(NIPH)(Bim)2]n (2)
X-Ray crystal structure determinations
A mixture of Co(CH3COO)2 ·4H2O (0.125 g, 0.5 mmol), H2NIPH
(0.106 g, 0.5 mmol)), Bim (0.120 g, 1 mmol), and H2O (10 mL) was
stirred for 30 min and heated at 140 °C for 72 hours in a Teflon-
lined stainless steel autoclave (25 mL) under autogenous pressure.
After cooling to room temperature, block-shaped crystals were ob-
tained. The yield was 50 % based on Co. Element analysis calcd
for C22H15N5O6Co: C 52.40; H 3.0; N 13.89 %; found: C 52.26; H
2.89; N 14.08 %. IR (KBr, cmϪ1) data: 3083(w), 1614(vs), 1564(m),
1528(s), 1433(m), 1354(vs), 1275(w), 1255(w), 1186(w), 1104(w),
975(w), 930(w), 781(m), 732(s), 620(m).
The crystal structures of 1Ϫ4 were determined by single-crystal X-
ray diffraction experiment. The reflection data were collected on a
Rigaku R-AXIS RAPID diffractometer (Mokα radiation, graphite
monochromator) at room temperature with ω-scan mode. Empiri-
cal absorption correction was applied for all data. The structure
was solved by direct methods and refined by full-matrix least
squares on F2 using SHELXTL97 software [19]. The heaviest
atoms were firstly located. O and C atoms were subsequently lo-
cated in difference Fourier maps. All non-hydrogen atoms were re-
fined anisotropically. The hydrogen atoms of 1Ϫ4 were located
based on theoretical riding models except those in water molecules
of 4. Experimental details for the structure determination are given
in Table 1. The selected bond distances and angles are tabulated in
Table 2. The hydrogen bonds are listed in Table 3.
Preparation of [Zn(NIPH)(Bim)]n (3)
The title compound was prepared by the same procedure as the
synthesis of 1. The yield was 52 % based on Zn. Element analysis
calcd for C15H9N3O6Zn: C 45.89; H 2.31; N 10.70 %; found: C
45.71; H 2.26; N 10.84 %. IR (KBr, cmϪ1) data: 3194(w), 1630(s),
1571(m), 1535(m), 1455(w), 1367(vs), 1255(w), 1153(w), 1077(m),
982(w), 926(m), 791(w), 728(vs), 607(m).
Results and Discussion
Crystal structure [Cu(NIPH)(Bim)2]n (1)
Single structure analysis reveals that 1 displays a zig-zag
chain structural feature. In the asymmetric unit, there are
two Cu cations, two NIPH and four Bim ligands (Fig. 1).
Both Cu1 and Cu2 are four-coordinated in a slightly dis-
torted quadrate plane geometry [CuO2N2], i.e. each Cu
atom bonds with two carboxyl-oxygen atoms from two dif-
ferent NIPH ligands and two nitrogen atoms from two dif-
Preparation of [Cd(NIPH)(Bim)(H2O)]n (4)
The title compound was prepared by the same procedure as the
synthesis of 2. The yield was 60 % based on Cd. Element analysis
calcd for C15H11N3O7Cd: C 39.37; H 2.42; N 9.18 %; found: C
39.18; H 2.26; N 9.23 %. IR (KBr, cmϪ1) data: 3379(m), 1607(vs),
Table 1 Crystal data and structure refinement for 1Ϫ4.
1
2
3
4
Empirical formula
Formula weight
Crystal system
Space group
C22H15N5O6Cu
508.93
C22H15N5O6Co
504.32
monoclinic
C2/c
17.785(4)
10.345(2)
23.744(5)
90
110.12(3)
90
4102.1(14)
8
1.633
0.51ϫ0.23ϫ0.1
0ՅhՅ22
Ϫ13ՅkՅ13
Ϫ30ՅlՅ28
0.0309
C15H9N3O6Zn
392.62
C15H11N3O7Cd
457.67
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
˚
a (A)
12.512(3)
12.994(3)
13.599(3)
74.74(3)
86.44(3)
85.92(3)
2125.5(7)
4
8.7060(17)
9.6354(19)
10.139(2)
61.99(3)
84.02(3)
77.46(3)
732.9(2)
2
8.1422(16)
10.085(2)
11.723(2)
69.99(3)
76.93(3)
67.68(3)
831.6(3)
2
˚
b (A)
˚
c (A)
Ͱ (°)
β (°)
γ (°)
3
˚
Volume (A )
Z
Dc (mg/m3)
Crystal size (mm)
1.590
1.779
1.828
0.26ϫ0.17ϫ0.1
Ϫ16ՅhՅ16
Ϫ16ՅkՅ16
Ϫ17ՅlՅ17
0.0344
0.43ϫ0.28ϫ0.1
0ՅhՅ11
Ϫ11ՅkՅ12
Ϫ12ՅlՅ13
0.0359
0.43ϫ0.16ϫ0.1
0ՅhՅ10
Ϫ11ՅkՅ13
Ϫ14ՅlՅ15
0.0235
Limiting indices
Rint
Data / restraints / parameters
9577 / 0 / 733
1.079
1036
1.005
0.0446
0.1315
0.0632
0.1458
0.454, Ϫ0.356
4554 / 0 / 307
0.890
2056
1.012
0.0325
0.0771
0.0486
0.0828
0.292, Ϫ0.270
3276 / 0 / 226
1.717
396
1.038
0.0332
0.0877
0.0384
0.0897
0.442, Ϫ0.538
3675 / 0 / 243
1.358
452
1.031
0.0231
0.0619
0.0287
0.0714
0.691, Ϫ0.763
µ (mmϪ1
F (000)
)
GoF on F2
R1 [I>2σ(I)]a
wR2 [I>2σ(I)]a
R1 (all data)a
wR2 (all data)a
Ϫ3
˚
Largest diff. peak and hole (e. A
)
a R1 ϭ ΣʈFo ͉Ϫ͉Fc ʈ/Σ͉Fo ͉; wR2 ϭ {Σ[w(Fo2ϪFc2 )2 ]/Σ[w(Fo2)]2 }1/2
346
www.zaac.wiley-vch.de
 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 345Ϫ351

Coordination Polymers Constructed from 5-Nitroisophthalate and Benzimidazole Ligand
˚
˚
Table 2 Selected bond lengths /A and angles /° for 1Ϫ4.
Table 3 Hydrogen bonds for 1Ϫ4 /A and °.
1
D-H···A
d(D-H)
d(H···A)
d(D···A)
<(DHA)
Cu(1)-O(2)
Cu(1)-N(4)
Cu(1)-N(2)
Cu(1)-O(7)
O(2)-Cu(1)-N(2)
O(7)-Cu(1)-N(2)
O(7)-Cu(1)-N(4)
N(2)-Cu(1)-N(4)
O(3)i-Cu(2)-N(8)
1.961(2)
1.986(3)
1.984(3)
1.9701(19)
87.69(10)
93.83(10)
88.39(10)
161.34(12)
93.14(11)
Cu(2)-N(10)
Cu(2)-O(9)
1.959(3)
1.967(2)
1.941(2)
1.965(3)
166.76(9)
94.37(10)
1
N(3)-H(3)···O(8)i
N(5)-H(5)···O(4)ii
N(7)-H(7)···O(1)iii
N(9)-H(9)···O(10)iv
C(35)-H(35)···O(8)iii
C(33)-H(33)···O(5)v
C(44)-H(44)···O(12)vi
C(11)-H(11)···O(10)vii
C(10)-H(10)···O(10)vii
C(20)-H(20)···O(4)viii
C(15)-H(15)···O(11)ix
0.71(4)
0.76(6)
0.72(4)
0.75(5)
0.92(4)
0.92(4)
0.78(4)
0.88(4)
0.86(4)
0.94(5)
0.97(4)
2.05(4)
2.26(5)
2.05(4)
2.00(5)
2.64(4)
2.66(4)
2.63(4)
2.69(4)
2.72(3)
2.69(5)
2.59(4)
2.734(4)
2.837(4)
2.747(5)
2.750(4)
3.483(5)
3.293(5)
3.286(4)
3.256(5)
3.225(4)
3.501(6)
3.285(4)
162(4)
132(5)
162(4)
174(6)
151(3)
127(3)
142(3)
123(3)
119(3)
146(4)
129(3)
Cu(2)-O(3)i
Cu(2)-N(8)
O(2)-Cu(1)-O(7)
O(2)-Cu(1)-N(4)
O(3)i-Cu(2)-N(10) 94.01(10)
O(3)i-Cu(2)-O(9)
N(10)-Cu(2)-N(8)
N(8)-Cu(2)-O(9)
158.08(9)
159.39(11)
88.98(11)
N(10)-Cu(2)-O(9) 91.54(10)
2
Co(1)-O(4)i
1.9793(14)
1.9875(15)
114.96(7)
106.17(7)
112.51(7)
Co(1)-N(4)
2.0136(17)
2.0186(17)
110.88(7)
105.24(6)
106.88(6)
Co(1)-O(1)
Co(1)-N(2)
2
O(1)-Co(1)-N(4)
O(1)-Co(1)-N(2)
N(4)-Co(1)-N(2)
O(4)i-Co(1)-N(2)
O(4)i-Co(1)-O(1)
O(4)i-Co(1)-N(4)
N(3)-H(3A)···O(3)i
N(5)-H(5A)···O(2)ii
N(5)-H(5A)···O(5)iii
C(6)-H(6)···O(4)iv
C(4)-H(4)···O(1)v
0.86
0.86
0.86
0.93
0.93
1.85
1.94
2.62
2.69
2.65
2.693(3)
2.681(2)
3.183(3)
3.567(2)
3.562(2)
166.1
143.8
124.4
157.2
168.8
3
Zn(1)-O(1)
Zn(1)-O(4)i
N(2)-Zn(1)-O(4)i
N(2)-Zn(1)-O(3)ii
1.9309(15)
1.9860(17)
108.91(7)
110.41(8)
Zn(1)-N(2)
1.9781(18)
1.9916(16)
99.59(7)
104.34(7)
122.83(8)
Zn(1)-O(3)i
3
O(1)-Zn(1)-O(3)ii
O(1)-Zn(1)-O(4)i
O(1)-Zn(1)-N(2)
N(3)-H(3A)···O(2)i
N(3)-H(3A)···O(6)ii
C(11)-H(11)···O(3)i
0.86
0.86
0.93
2.06
2.69
2.68
2.877(3)
3.076(3)
3.508(3)
157.5
108.5
148.5
O(4)i-Zn(1)-O(3)ii 110.07(8)
4
4
Cd(1)-N(2)
2.250(2)
2.384(2)
2.364(2)
121.81(8)
133.65(7)
91.20(8)
81.69(9)
Cd(1)-O(4)i
Cd(1)-O(1)
Cd(1)-O(2)
2.2541(18)
2.501(2)
2.3311(19)
93.61(8)
154.71(7)
83.44(7)
92.81(8)
84.63(7)
84.16(8)
99.44(7)
N(3)-H(3A)···O(5)i
O(7)-H(7A)···O(1)ii
O(7)-H(7B)···O(4)iii
C(9)-H(9)···O(3)iv
0.86
2.23
2.966(3)
2.708(3)
2.783(3)
3.054(3)
143.8
158(4)
168(4)
129.9
Cd(1)-O(3)ii
0.89(4)
0.78(4)
0.93
1.86(4)
2.02(4)
2.37
Cd(1)-O(7)
N(2)-Cd(1)-O(4)i
O(4)i-Cd(1)-O(2)
N(2)-Cd(1)-O(7)
O(2)-Cd(1)-O(7)
O(2)-Cd(1)-O(3)ii
N(2)-Cd(1)-O(1)
O(4)i-Cd(1)-O(1)
O(7)-Cd(1)-O(1)
O(3)ii-Cd(1)-O(1)
O(4)i-Cd(1)-O(7)
O(4)i-Cd(1)-O(3)ii
Symmetry transformations used to generate equivalent atoms: For 1:
i Ϫxϩ1, Ϫyϩ1, Ϫzϩ1; ii x, yϩ1, z; iii Ϫxϩ1, Ϫyϩ2, Ϫz; iv Ϫx, Ϫyϩ2,
Ϫzϩ1; v Ϫxϩ1, Ϫyϩ1, Ϫz; vi xϪ1, y, z; vii Ϫxϩ1, Ϫyϩ2, Ϫzϩ1; viii Ϫxϩ2,
Ϫyϩ1, Ϫz; ix x, yϪ1, z. For 2: i Ϫxϩ1, Ϫy, Ϫzϩ2; ii Ϫxϩ1, Ϫyϩ1, Ϫzϩ2;
iii xϩ1/2, Ϫyϩ1/2, zϩ1/2; iv Ϫxϩ1/2, yϩ1/2, Ϫzϩ3/2; v Ϫxϩ1/2, yϪ1/2,
Ϫzϩ3/2. For 3: i Ϫxϩ1, Ϫyϩ2, Ϫzϩ1; ii xϪ1, yϩ1, z. For 4: i xϪ1, yϪ1,
zϩ1; ii Ϫxϩ2, Ϫyϩ1, Ϫzϩ1; iii Ϫxϩ2, Ϫyϩ2, Ϫzϩ1; iv x, yϪ1, z.
N(2)-Cd(1)-O(3)ii 89.47(8)
O(7)-Cd(1)-O(3)ii
N(2)-Cd(1)-O(2)
O(2)-Cd(1)-O(1)
175.28(7)
102.44(8)
53.64(7)
Symmetry transformations used to generate equivalent atoms: For 1: i xϪ1,
yϩ1, z . For 2: i xϩ1/2, yϩ1/2, z. For 3: i x, y, zϩ1; ii Ϫxϩ1, Ϫyϩ1, Ϫzϩ1.
For 4: i x, y-1, z; ii -xϩ1, -yϩ2, -zϩ1.
and carboxyl-oxygen of NIPH ligands. The C-H···O hydro-
gen bonds involve the nitro and carboxyl groups and C-H
groups of Bim molecules. Additionally, there are π···π stack-
ing interactions between two adjacent aromatic rings of the
ferent Bim ligands. The Cu-N distances range from
˚
˚
1.959(3) A to 1.986(3) A, and Cu-O distances range from
˚
˚
1.941(2) A to 1.9701(19) A. The angles vary from
158.08(9)° to 166.76(9)° for O-Cu-O and from 87.69(10)° to
94.37(10)° for O-Cu-N. In addition, weak intra-chain inter-
actions between Cu atoms and the oxygen atoms from
NIPH exist in the axial direction due to the Jahn-Teller
˚
Bim molecules with distance of 3.62 A.
Crystal structure [Co(NIPH)(Bim)2]n (2)
˚
effect with acceptable Cu···O distances [Cu1···O8, 2.793 A,
˚
and Cu2···O10, 2.676 A]. Similar Cu···O contact distances
Compound 2 presents a straight line chain structure. In the
asymmetric unit, there are one Co cation, one NIPH and
two Bim ligands. Each Co is tetrahedrally coordinated [Co-
in the axial direction were also found in some CuII com-
˚
pounds, such as [Cu2(ipO)(4,4Ј-bpy)] (Cu-O ϭ 2.594 A);
˚
˚ ˚
O1, 1.9875(15) A; Co-O4A, 1.9793(14) A; Co-N2,
[Cu(pyta)2(H2O)·0.5H2O)]n (Cu-O ϭ 2.723 A); [Cu2(2,2-
˚
˚
˚
bpy)3(3,5-PDC)]2(ClO4)42(H2O) (Cu-O ϭ 2.522 A and
2.0186(17) A; Co-N4, 2.0136(17) A] with angles of O-Co-
O: 105.24(6)°, N-Co-N: 112.51(7)°, and the O-Co-N angles
range from 106.17(7)° to 114.96(7)° (Fig. 2), which is differ-
ent from distorted quadrate plane geometry around Cu cat-
ions in 1. As a µ2-bridge (Scheme 1a), NIPH ligands adopt
bis-monodentate mode and link Co atoms into a straight
line chain (Fig. 5b) and the distance between two adjacent
˚
2.724 A) [20].
In compound 1, NIPH ligand adopts bis-monodentate
mode (Scheme 1a) and links Cu atoms to form an infinite
single zig-zag chain (Fig. 5a). Each Bim ligand, as a ter-
minal ligand, occupies two coordination positions of the Cu
atom and decorates alternately at two sides of chains. The
zig-zag chains are further packed into a 3D architecture
through hydrogen bonding and π···π stacking interactions
(Fig. 6a). For two adjacent chains, there are N-H···O hydro-
gen bonding interactions between the N-H groups of Bim
˚
Co atoms bridged by a NIPH ligand is 10.287 A. All
straight line chains assemble into a three-dimensional
framework based on N-H···O and C-H···O hydrogen bond-
ing interactions (Fig. 6b).
Z. Anorg. Allg. Chem. 2008, 345Ϫ351
 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
347

J.-W. Ye, D. Li, K.-Q. Ye, Y. Liu, Y.-F. Zhao, P. Zhang
Fig. 2 Perspective view of the coordination environment around
CuII ion with thermal ellipsoids at 30% probability level in 2.
dinated carboxyl-oxygen atom and a nitro-oxygen atom
˚
˚
(N3···O2, 2.877(3) A and N3···O6, 3.076(3) A), while the
C-H···O hydrogen bond involves a C-H group of Bim and
a coordinated carboxyl-oxygen atom with C11···O3 dis-
˚
tance of 3.508(3) A.
Crystal structure [Cd(NIPH)(Bim)(H2O)]n (4)
Fig. 1 Perspective views of the coordination environment around
CuII ions with thermal ellipsoids at 30% probability level in 1.
The 4 exhibits a double-stranded loop-like chain structure
similar to 3. In 4, the coordination geometry of Cd cation
is in a distorted octahedron formed by four carboxylate
˚
oxygen atoms [Cd1-O4B, 2.2541(18) A; Cd1-O2,
˚
˚
˚
2.3311(19) A; Cd1-O3A, 2.384(2) A; Cd1-O1, 2.501(2) A]
from three different NIPH ligands, one nitrogen atom [Cd1-
˚
N2, 2.250(2) A] of a Bim ligand and one water molecule
oxygen [Cd1-O7 2.364(2) A] (Fig. 4). All Cd-O bond dis-
˚
tances are in good agreement with those found in other
extended structures constructed from NIPH ligands
[16Ϫ18]. Two carboxylate groups of NIPH coordinate with
Scheme 1 The coordination modes of NIPH ligand: (a) in 1 and
2; (b) in 3; (c) in 4.
Crystal structure [Zn(NIPH)(Bim)]n (3)
In compound 3, the central Zn cation is tetrahedrally coor-
dinated by three carboxylate-oxygen atoms from three dif-
ferent NIPH ligands and one nitrogen atom of one Bim
ligand (Fig. 3). The Zn-O and Zn-N bond distances
˚
˚
[Zn1-O1, 1.9309(15) A; Zn1-O3A, 1.9916(16) A; Zn1-O4B,
˚
˚
1.9860(17) A and Zn-N2 1.9781(18) A] are very similar to
that reported in Zn-polycarboxylate compounds [16, 21].
As µ3-bridging ligand, NIPH connects three Zn atoms
(Scheme 1b). A double-stranded loop-like chain (Fig. 5c) is
formed by sharing NIPH ligands and Zn2 subunit which is
connected through two carboxylic groups and two Zn ions.
The terminal Bim ligands decorate alternately at two sides
of the chains, which assembly into three-dimensional archi-
tecture based on N-H···O and C-H···O hydrogen bonding
interactions (Fig. 6c). The N-H group of Bim as a donor
forms two kinds of N-H···O hydrogen bonds with a uncoor-
Fig. 3 Perspective view of the coordination environment around
ZnII ion with thermal ellipsoids at 30% probability level in 3.
348
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Z. Anorg. Allg. Chem. 2008, 345Ϫ351

Coordination Polymers Constructed from 5-Nitroisophthalate and Benzimidazole Ligand
three Cd atoms in 4 (Scheme 1c). The dinuclear Cd2 subun-
its are further interconnected by benzene rings of NIPH to
form a double-stranded loop-like chain structure (Fig. 5d).
A 3D structure of 4 is constructed by inter-chain hydrogen
bonds (Fig. 6d). There are three types of hydrogen bonds
in 4. The first type of hydrogen bond is N-H···O between
N-H groups of Bim ligands and nitro-oxygen atoms of
˚
NIPH with N3···O5 distance of 2.966(3) A, the second one
is O-H···O between O-H groups of water molecules and co-
ordination carboxyl-oxygen atoms of NIPH with O7···O1
˚
˚
distance of 2.708(3) A and O7···O4 distance of 2.783(3) A,
and the third one is C-H···O between C-H groups of Bim
ligands and carboxyl-oxygen atoms of NIPH with C9···O3
˚
distance of 3.054(3) A (Fig. 6d).
Fig. 5 Perspective views of the zig-zag single chain of 1 (a); line-
like single chain of 2 (b); and loop-like double-stranded chain of 3
(c) and 4 (d).
Fig. 4 Perspective view of the coordination environment around
CdII ion with thermal ellipsoids at 30% probability level in 4.
Thermogravimentric analyses
The thermal properties of 1Ϫ4 were studied by thermograv-
imetric analyses (TGA) in air. The TGA results indicate
that 1, 2 and 3 begin to decompose at 267, 301 and 375 °C,
respectively. For 4, the first weight loss of 4.19 % from 105
to 220 °C is in accordance with the loss of water molecules
(calcd 3.94 %), while the second weight loss corresponds to
that of Bim and NIPH ligands.
Fig. 6 Views of the hydrogen-bonded three-dimensional supramo-
lecular networks of 1 (a), 2 (b), 3 (c) and 4 (d).
Magnetic property of 1
The temperature dependent magnetic behaviors of 1 were
investigated and magnetic susceptibility data were collected
in the temperature range from 2 to 300 K. The susceptibility
curve of χm and χmT versus T plots in the full temperature
range for 1 is presented in Figure 7. At room temperature
the effective magnetic moment per metal atom of 1 is
1.85 µB, which is slightly higher than the spin-only value of
mononuclear S ϭ 1/2 ground CuII ions (theoretical value
for µeff ϭ 1.73 µB). The χmT value is 0.430 cm3 ·K·molϪ1 at
300 K and upon cooling slowly decreased to the value of
0.398 cm3 ·K·molϪ1 at 2 K. This fact indicates the charac-
teristic of weak antiferromagnetic interactions in 1. The
plot of χmϪ1 vs. T over the temperature agrees with the Cu-
rie-Weiss law χm ϭ Cm/(T-Θ). The magnetic behavior of
Z. Anorg. Allg. Chem. 2008, 345Ϫ351
 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
349

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In this paper, we have successfully synthesized four coordi-
nation polymers [Cu(NIPH)(Bim)2]n (1), [Co(NIPH)-
(Bim)2]n (2), [Zn(NIPH)(Bim)]n (3), and [Cd(NIPH)(Bim)-
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type motifs, i.e. zig-zag chains for 1, straight line chains for
2, double-stranded loop-like chains for 3 and 4. The chains
are assembled into three-dimensional networks based on
hydrogen-bonds. The structural investigation of these com-
pounds indicates that different metal ions and coordination
modes of organic ligands have important influence on the
structural diversities. The weak antiferromagnetic coupled
interaction exists in 1 upon decreasing temperature.
Supplementary material: X-ray crystallographic files in CIF format
deposited with the Cambridge Structural Database as files CCDC-
610093, 607592, 607593, 607594, respectively, for crystals 1Ϫ4.
These data can be obtained free of charge via www.ccdc.cam.ac.uk/
conts/retrieving.html [or from the Cambridge Crystallographic
Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; Fax:
(internat.) ϩ44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk]
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