Two new polymers constructed from bisdentate function of the 4,4'-bipyridine and 4-sulfobenzoate

Article abstract of DOI:10.1080/15533170701608940

Two new 4-sulfobenzoate coordination polymers based on the Zn2+/Cd2+/4-sulfobenzoate/4,4'-bipyridine system, [Zn(4,4'-bipy) (H2O)4] (sb) (1), [Cd2(4,4'-bipy)4(sb)2(H2O)3]3H2O (2) [4,4'-bipy=4,4'-bipyridine; sb=4-sulfobenzoate dianion], have been prepared and characterized by IR, elemental analysis and single-crystal X-ray analysis. Their X-ray crystal structures show that the two complexes belong to a orthorhombic system, Pca21 space group, a=12.1794(8) , b=11.3422(8) , c=14.7572(10) and a monoclinic system, C/c space group, =101.161(2), a=12.4916(16)) , b=19.023(2) , c=23.501(3) for 1 and 2, respectively. Both of the complexes form 1-D chains, while the arrangement of the 1-D chains are different. In contrast to monodentate 4,4'-bipy-containing complexes reported in the literature, the bisdentate function for 4,4'-bipy in 4-sulfobenzoate transition metal system has not been reported up to now. Extensive hydrogen-bonding interactions in the 2 complexes control their crystal packing and give rise to 3D extended supramolecular networks.

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Two New Polymers Constructed from Bisdentate
Function of the 4,4′‐Bipyridine and 4‐Sulfobenzoate
Lu‐Fang Ma a , Jian‐Qiang Liu b & Li‐Ya Wang c
a Department of Chemistry , Luoyang Normal University , Luoyang, P. R. China
b Department of Chemistry, Shaanxi Key Laboratory of Physico‐Inorganic Chemistry ,
Northwest University , Xi'an, P. R. China
c Department of Chemistry , Luoyang Normal University , Luoyang, P. R. China
Published online: 01 Oct 2007.
To cite this article: Lu‐Fang Ma , Jian‐Qiang Liu & Li‐Ya Wang (2007) Two New Polymers Constructed from Bisdentate Function
of the 4,4′‐Bipyridine and 4‐Sulfobenzoate, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry,
37:8, 647-652
To link to this article: http://dx.doi.org/10.1080/15533170701608940
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 37:647–652, 2007
Copyright # 2007 Taylor & Francis Group, LLC
ISSN: 1553-3174 print/1553-3182 online
DOI: 10.1080/15533170701608940
Two New Polymers Constructed from Bisdentate Function
of the 4,40-Bipyridine and 4-Sulfobenzoate
Lu-Fang Ma
Department of Chemistry, Luoyang Normal University, Luoyang, P. R. China
Jian-Qiang Liu
Department of Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest
University, Xi’an, P. R. China
Li-Ya Wang
Department of Chemistry, Luoyang Normal University, Luoyang, P. R. China
4-pyridyl donor units interconnected by chain or groups of
Two new 4-sulfobenzoate coordination polymers based on the different class, such as pyrazine, 4,40-bipyridine, and 4,40-azo-
Zn21/Cd21/4-sulfobenzoate/4,40-bipyridine system, [Zn(4,40-bipy)
bispyridine. Numerous polymeric transition metal complexes
0
0
.
(H2O)4] (sb) (1), [Cd2(4,4 -bipy)4(sb)2(H2O)3] 3H2O (2) [4,4 -
bipy 5 4,40-bipyridine; sb 5 4-sulfobenzoate dianion], have been
prepared and characterized by IR, elemental analysis and single-
crystal X-ray analysis. Their X-ray crystal structures show that the
with 4,40-bipy have been synthesized and structurally charac-
terized to date.[3–8] It should be noteworthy that the weaker
intermolecular forces, especially hydrogen bonds, play an
two complexes belong to a orthorhombic system, Pca21 space important role in fundamental biological self-assembly
process.[9–12] Thus, rationally utilizing weaker intermolecular
forces to build up novel supramolecular networks is still an
appealing filed for chemists. For this reason, we introduced a
new assistant 4-sulfobenzoate (sb) ligand, which has potential
˚
group, a 5 12.1794(8) A, b 5 11.3422(8) A, c 5 14.7572(10) A and
a monoclinic system, C/c space group, b 5 101.161(2)8, a 5
˚
˚
˚
˚
˚
12.4916(16)) A, b 5 19.023(2) A, c 5 23.501(3) A for 1 and 2,
respectively. Both of the complexes form 1-D chains, while the
arrangement of the 1-D chains are different. In contrast to mono-
dentate 4,40-bipy-containing complexes reported in the literature, coordinate sites due to the combination of carboxyl-and
the bisdentate function for 4,40-bipy in 4-sulfobenzoate transition
metal system has not been reported up to now. Extensive
sulfonic group. Furthermore, bearing in mind that the
sulfonic bond would be able to stabilize the network. On the
other hand, there is no example of bisdentate 4,40-bipyridine
hydrogen-bonding interactions in the 2 complexes control their
crystal packing and give rise to 3D extended supramolecular
networks.
mode in the 4-sulfobenzoate transition metal (II) complexes.
Several coordination modes or existing form of the 4,40-bipyr-
idine in all previously reported 4,40-bipyridine-containing
4-sulfobenzoate metal complexes, in which 4,40-bipyridine
adopts monodentate fashion.[6,13] Here, we report syntheses
and crystal structures of 2 d10 metal complexes favorably
incorporating bisdentate 4,40-bipyridine.
Keywords 4-sulfobenzoate, 4,40-bipyridine, crystal structure,
hydrogen bond
INTRODUCTION
The development of inorganic supramolecular architectures
is a rapidly developing area of research that has implications
for rational design of functional materials.[1,2] A particularly
classical ligands is represented by molecules containing two
EXPERIMENTAL
Materials and Physical Measurements
All reagents used in the syntheses were of analytical grade.
Elemental analyses for carbon, hydrogen and nitrogen were
performed on a Vario EL III elemental analyzer. The infrared
spectra (4000–600 cm21) were recorded by using KBr pellet
on an Avatar 360 E. S. P. IR spectrometer. The crystal determi-
nation was performed on a Bruker SMART APEX II CCD dif-
fractometer equipped with graphite-monochromatized MoKa
Received 15 April 2007; accepted 5 June 2007.
This work was supported by the Natural Science Foundation of
China (No. 20471026) and the Foundation of Education Committee
of Henan province (No. 2006150017).
Address correspondence to Li-Ya Wang, Department of Chemistry,
Luoyang Normal University, Luoyang 471022, P. R. China. E-mail:
wlya@lynu.edu.cn
˚
radiation (l ¼ 0.71073 A).
647

648
L.-F. MA ET AL.
TABLE 1
Crystallographic data for 1 and 2
Empirical formula
Formula weight
Temperature (K)
C17H22N2O10SZn
601.8
291(2)
C54H52Cd2N8O16S2
1357.96
291(2)
˚
Wavelength (A)
0.71073
Orthorhombic
Pca21
0.71073
Monoclinic
C c
Crystal system
Space group
Unit cell dimensions
˚
˚
a ¼ 12.1794(8) A
a ¼ 12.4916(16) A
˚
˚
b ¼ 11.3422(8) A
b ¼ 19.023(2) A
˚
˚
c ¼ 14.7572(10) A
c ¼ 23.501(3) A
b ¼ 101.161(2)8
3
˚
2038.6(2) A, 2
Volume, Z
Calculated density (Kg/m3)
Crystal size (mm3)
5478.9(12), 4
1.646
1.668
0.40 ꢀ 0.19 ꢀ 0.09
0.46 ꢀ 0.29 ꢀ 0.16
u Range for data collection (º)
Reflections collected
Independent reflection
Final R indices [I . 2s (I)]
R indices (all data)
2.45–27.50
11649
2.43–25.50
13805
4582 [Rint ¼ 0.0292]
R1 ¼ 0.0419, wR2 ¼ 0.1125
R1 ¼ 0.0529, wR2 ¼ 0.1208
9117 [Rint ¼ 0.0284]
R1 ¼ 0.0402, wR2 ¼ 0.0909
R1 ¼ 0.0627, wR2 ¼ 0.1033
Synthesis of Complexes
1143(m), 1052(m), 1036(s), 1007(s), 810(s), 752(s), 650(m).
Anal. (%) Calc. for C17H22N2O10SZn: C, 39.89; H, 4.33; N,
5.47. Found: C, 39.78; H, 4.46; N, 5.63. IR (KBr, cm21) for
2: 3376(m), 1583(s), 1525(m), 1501(w), 1423(m), 1318(m),
1283(s), 1179(m), 1143(m), 1052(m), 1036(s), 1009(s),
The title compounds were prepared through the hydrother-
mal conditions. In a typical experiment, 4,40-bipyridine
(0.168 g, 1.088 mmol) in an aqueous solution (10 mL) of
NaOH (0.040 g, 1 mmol) was mixed with an aqueous
solution (8 mL) of ZnCl2 (0.2 g, 1.47 mmol) or
816(s),
752(s),
656(m).
Anal.
(%)
Calc.
for
.
CdSO4 5H2O (0.279 g, 0.093 mmol) and potassium
C54H52Cd2N8O16S2: C, 47.76; H, 3.83; N, 8.25. Found: C,
47.89; H, 3.76; N, 8.29.
hydrogen 4-sulfobenzoate (0.120 g, 0.5 mmol). After stirring
for 5 min in air, triethylamine (0.5 mmol) was added and
then the mixture was placed into 25 mL Teflon-lined autoclave
and heated at 1408C for 48 h. The autoclave was cooled over a
period of 12 h at a rate of 58C h21. 1 and 2 as colorless pris-
Crystallographic Data Collection and Structures
Determination
Single crystal X-ray diffraction analysis of the 2 complexes
matic crystal was collected by filtration, washed with water, were carried out. A colorless single crystal of the complex 1 or
and dried in air. IR (KBr, cm21) for 1: 3372(m), 1592(s), 2 was put on a Bruker SMART APEX II CCD diffractometer
1523(m), 1501(w), 1422(m), 1318(m), 1279(s), 1189(s), equipped with a graphite monochromated MoKa radiation
TABLE 2
˚
Selected bond lengths (A) and angles (º) for 1
Zn(1)-O(3)
Zn(1)-N(2)
Zn(1)-O(1)
2.108(3)
2.113(3)
2.131(3)
2.133(3)
2.143(3)
2.147(3)
91.28(13)
178.05(12)
90.52(13)
86.63(14)
N(2)-Zn(1)-N(1)#1
O(1)-Zn(1)-N(1)#1
O(3)-Zn(1)-O(2)
N(2)-Zn(1)-O(2)
O(1)-Zn(1)-O(2)
N(1)#1-Zn(1)-O(2)
O(3)-Zn(1)-O(4)
N(2)-Zn(1)-O(4)
O(1)-Zn(1)-O(4)
N(1)#1-Zn(1)-O(4)
177.88(19)
91.58(14)
91.82(14)
92.60(15)
88.86(14)
87.14(18)
93.58(14)
91.62(16)
85.62(14)
88.84(18)
Zn(1)-N(1)#1
Zn(1)-O(2)
Zn(1)-O(4)
O(3)-Zn(1)-N(2)
O(3)-Zn(1)-O(1)
N(2)-Zn(1)-O(1)
O(3)-Zn(1)-N(1)#1
Symmetry transformations used to generate equivalent atoms: #1 x, y þ 1, z; #2 x, y 2 1, z.

NEW 4-SULFOBENZOATE COORDINATION POLYMERS
649
TABLE 3
o
Selected bond lengths (A) and angles ( ) for 2
˚
Cd(1)-N(7)
Cd(1)-N(2)
2.330(3)
2.344(2)
2.402(3)
2.420(3)
2.424(3)
2.532(3)
2.540(3)
2.306(3)
2.316(3)
2.339(3)
2.365(2)
2.367(4)
2.376(4)
90.24(16)
83.73(9)
139.43(15)
92.73(10)
136.66(15)
83.81(9)
175.38(9)
84.40(15)
92.66(10)
84.00(10)
97.03(9)
O(2)-Cd(1)-O(1)
O(6)-Cd(1)-O(1)
N(8)#1-Cd(1)-O(1)
O(7)-Cd(1)-O(1)
N(3)-Cd(2)-O(11)
N(3)-Cd(2)-N(5)
O(11)-Cd(2)-N(5)
N(3)-Cd(2)-N(1)
O(11)-Cd(2)-N(1)
N(5)-Cd(2)-N(1)
N(3)-Cd(2)-O(13)
O(11)-Cd(2)-O(13)
N(5)-Cd(2)-O(13)
N(1)-Cd(2)-O(13)
N(3)-Cd(2)-O(12)
O(11)-Cd(2)-O(12)
N(5)-Cd(2)-O(12)
N(1)-Cd(2)-O(12)
O(13)-Cd(2)-O(12)
N(2)-Cd(1)-N(8)#1
O(2)-Cd(1)-O(7)
O(6)-Cd(1)-O(7)
N(8)#1-Cd(1)-O(7)
N(7)-Cd(1)-O(1)
53.33(9)
137.14(10)
96.54(10)
170.54(8)
88.94(13)
176.76(14)
88.60(12)
89.97(15)
89.37(17)
92.11(15)
90.59(12)
174.03(10)
92.07(12)
84.68(16)
89.31(13)
108.86(14)
89.49(14)
161.73(19)
77.08(13)
94.37(16)
136.13(10)
52.32(10)
83.56(10)
83.64(9)
Cd(1)-O(2)
Cd(1)-O(6)
Cd(1)-N(8)#1
Cd(1)-O(7)
Cd(1)-O(1)
Cd(2)-N(3)
Cd(2)-O(11)
Cd(2)-N(5)
Cd(2)-N(1)
Cd(2)-O(13)
Cd(2)-O(12)
N(7)-Cd(1)-N(2)
N(7)-Cd(1)-O(2)
N(2)-Cd(1)-O(2)
N(7)-Cd(1)-O(6)
N(2)-Cd(1)-O(6)
O(2)-Cd(1)-O(6)
N(7)-Cd(1)-N(8)#1
N(2)-Cd(1)-O(7)
O(2)-Cd(1)-N(8)#1
O(6)-Cd(1)-N(8)#1
N(7)-Cd(1)-O(7)
Symmetry transformations used to generate equivalent atoms: #1 x, 2 y þ 2, z þ 1/2; #2 x, 2 y þ 2, z 2 1/2.
˚
(l ¼ 0.71073 A) by usingv 22u scan technique at room temp- located on a symmetry center and octahedrally coordinated
erature. The structures were solved by direct methods with with two N atoms of 2 separated 4,40-bipy in trans positions
SHELXS-97. The hydrogen atoms were assigned with and 4 aqua molecules. The Zn-O bond distances fall in the
˚
common isotropic displacement factors and included in the region 2.108(3)–2.147(3) A, and both Zn-N bond distances
˚
final refinement by use of geometrical restrains. A full- averaging 2.123 A are practically identical with the experimen-
matrix, least-squares refinement on F2 was carried out using tal limitation (Table 2). Thus, a Zn-4,40-bipy-Zn chain with
˚
. . .
SHELXL-97. The final agreement factor values are Zn
Zn separation 11.342 A is formed. The neighboring
˚
. . .
Zn distance is 7.388(5) A. The dihedral
R1 ¼ 0.0419, wR2 ¼ 0.1125 for
1
and R1 ¼ 0.0402, interchain Zn
wR2 ¼ 0.0909for 2, respectively. Table 1 shows crystallographic angle between the 2 pyridyl groups of the 4,40-bipy is 19.98,
crystal data of the complexes 1 and 2. Selected bond lengths and dissimilar to those observed in other polymers.[14–19]
angles are listed in Tables 2 and 3.
RESULTS AND DISCUSSION
Crystal Structure Description
[Zn(4,40-bipy)(H2O)4](sb) (1)
As shown in Figure 1, complex 1 is a cation-anion species,
which contains 1 Zn2þ cation, 1 bridging 4,40-bipyridine
ligand, 4 coordination water molecules and 1 lattice water
molecule, and 1 exoteric 4-sulfobenzoate dianion in asym-
metric unit. One 4,40-bipy molecule functions as a bridge to
connect 2 Zn2þ ions, leading to a 1-D covalently linked
chain running along the [100] direction. Each Zn2þ cation is
FIG. 1. Perspective drawings of the zinc (II) environment in 1.

650
L.-F. MA ET AL.
FIG. 3. Molecular structure of 2.
molecules as well as 3 aqua ligands to finish its octahedral
coordination environment. The Cd-O bond distances vary
FIG. 2. Simplified diagram of packing in 1.
˚
from 2.316 (3) to 2.540 (3) A, very similar to corresponding
distances in other cadmium complexes.[20] The dihedral
angle between the 2 pyridyl groups is 11.98 and 10.68 for the
monodentate 4,40-bipy and the bisdentate 4,40-bipy, respect-
ively, which are close to those in 1.
It should be pointed out that these adjacent zigzag chains are
further connected through hydrogen bonding between exoteric
4-sulfobenzoate dianion and 4,40-bipy molecule, leading to a
2-D structural sheet in the bc plane. Furthermore, the
adjacent layers are connected by the hydrogen bonds
between the lattice water molecule, coordinated water mol-
ecules and 4-sulfobenzoate dianion to afford 3D supramolecu-
lar structure (Fig. 2). Undoubtedly, the water molecules play an
important role in the stabilization of complex 1. These
It is worthy noting that there co-exists 2 coordination
fashion of 4,40-bipy, the monodentate 4,40-bipy ligands only
coordinate to the Cd1, which block the extending of the
high-dimensiomal structure to result a 1D architecture. In
contrast to complex 1 and previous reported complexes, the
4,40-bipy takes 2 coordination modes in 4-sulfobenzoate tran-
sition metal (II) complexes, which has not been reported up
to now. We speculate this phenomenon may be attributed to
the 2 coordinated modes of Cd atoms in this crystal. The
coordination polymers in both cases show 1-D chains; they
are diverse and can be obviously differentiated. In complex
˚
. . .
hydrogen bond parameters are: O1
. . .
O9 ¼ 2.772(4) AO(1)-
H(1W)
. . .
O2
O(9) ¼ 177.4(3)8; symmetry code: x,y þ 1,z;
˚
. . .
O5 ¼ 2.788(4) A O(2)-H(3W)
O(5) ¼ 167.4(4)8;
. . .
symmetry code: 2 x þ 1, 2 y þ 1, z 2 1/2; O2
O8 ¼ 2.838
˚
(6) A O(2)-H(4W)
. . .
O(8) ¼ 167.4(4)8 symmetry code: 2 x þ
˚
A
. . .
3/2,y þ 1,z þ 1/2; O3
O10 ¼ 2.691(4)
O(3)-H(5W)
O(10) ¼ 171.7(3)8; symmetry code: 2 x þ 3/2,y þ 1,z þ
˚
. . .
. . .
1/2; O4
. . .
O6 ¼ 2.711(4)] A O(4)-H(7W)
O(6) ¼ 139.58;
˚
. . .
O5
symmetry code: x,y 2 1,z þ 1.
O7 ¼ 2.645(5) A; O(5)-H(10W)
O(7) ¼ 127.7(2)8;
0
.
[Cd2(4,4 -bipy)4(sb)2(H2O)3] 3H2O (2)
X-ray crystallographic analysis shows that compound 2
exhibits a novel zigzag chain. As shown in Figure 3, there
are two independent Cd centers in the asymmetric units,
which appear in both hepta-Cd1 and hexa-coordinated Cd2
environment, showing distorted pentagonal bipyramidal and
octahedral coordination geometries, respectively. Cd1 com-
pletes its 7-coordination by 3 N atoms of 3 separated 4,40-
bipy and 4 carboxyl oxygen atoms from 2 chelating sb
ligands, while the 6-coordinated Cd2 connects to 3 4,40-bipy
FIG. 4. The overlapped chains in 2.

NEW 4-SULFOBENZOATE COORDINATION POLYMERS
651
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SUPPLEMENTARY MATERIAL
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Centre,
CCDC No. 632591 and 632592. Copies of this information
may be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: þ44-1223-336-033;
E-mail: deposit@ccdc.cam.ac.uk or http:// www.ccdc.cam.ac.uk).

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