Synthesis, structural characterization and properties of copper(II) and zinc(II) coordination polymers with a new bridging chelating ligand

Article abstract of DOI:10.1002/ejic.200400218

Two new coordination polymers [Cu₃(cpida)₂(H ₂O)₄]_n·4nH₂O (1) and [Zn(Hcpida)]_n·nH₂O (2) have been synthesized with a new bridging chelating ligand N-(4-carboxyphenyl)

Full text of DOI:10.1002/ejic.200400218

FULL PAPER
Synthesis, Structural Characterization and Properties of Copper(II) and
Zinc(II) Coordination Polymers with a New Bridging Chelating Ligand
Guo-Ping Yong,[a] Zhi-Yong Wang,*[a] and Yong Cui[a]
Keywords: Coordination polymers / Copper / N,O ligands / Zinc
Two new coordination polymers [Cu3(cpida)2(H2O)4]n·4nH2O
(1) and [Zn(Hcpida)]n·nH2O (2) have been synthesized with
nate open and closed channels along the a direction. The
dehydation and rehydration experiments showed that com-
a new bridging chelating ligand N-(4-carboxyphenyl)imino- pound 2 undergoes a reversible inclusion process to some
diacetic acid (H3cpida). X-ray diffraction analysis reveals that extent. However, the removal of guest water molecules from
complex 1 consists of 1D parallelogram-shaped molecular- 1 results in the collapse of the polymeric networks owing to
box chains constructed from unusual linear trinuclear CuII
secondary building units (SBUs), which further extend into
2D layers by perfect parallel AA stacking. Complex 2 adopts
a 2D framework comprised of tetrahedral ZnII centres iso-
lated from each other by the bridging bidentate carboxylate
the loss of the coordinated water molecules. Compound 2
also shows strong photoluminescence and may be a good
candidate for a photoactive or porous material.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
groups of the Hcpida2− ligands. Compound 2 possesses alter- Germany, 2004)
Introduction
tricarboxylate, the iminodiacetate group is more flexible
and can adopt different coordination modes; (b) the intro-
duced aromatic rings can offer additional πϪπ interactions
which may stabilize the frameworks.[10]
Metal-organic coordination polymers built up from me-
tallic clusters and multi-carboxylate building blocks have
been widely studied in recent years due to their interesting
topologies[1] and potential applications as functional mate-
rials.[2] The most commonly used strategy to obtain coordi-
nation polymers is to employ appropriate bridging ligands
that are capable of binding to several metal centres through
direct bond formation. Multi-carboxylate building blocks
with special configurations can yield desired networks in
metal-organic coordination polymers[3Ϫ5] because they can
act as either bridging or chelating ligands. A chelating li-
gand provides stronger connectivity and enhances rigidity
around the coordination centre, which results in higher sta-
bility of the resulting framework materials.[6] Thus, one of
the most necessary tasks of current research is the synthesis
of new bridging, chelating multi-carboxylate ligands be-
cause they have a pre-programmed tendency to form supra-
molecular motifs of defined geometry.[7Ϫ9] We are currently
focusing our attentions on the design and synthesis of new
bridging, chelating ligands and have recently obtained a
new bridging, chelating multi-carboxylate ligand N-(4-car-
boxyphenyl)iminodiacetic acid (H3cpida), which has two
important features: (a) unlike rigid groups such as benzene-
We describe here the synthesis, structural characteriz-
ation and properties of two new coordination polymers
[Cu3(cpida)2(H2O)4]n·4nH2O (1) and [Zn(Hcpida)]n·nH2O
(2) obtained from the H3cpida building block. Compound 1
is a rare 1D molecular-box chain constructed from unusual
linear trinuclear CuII SBUs. Compound 2 is a new 2D
framework constituted by tetrahedrally coordinated ZnII
with strong fluorescent emission.
Results and Discussion
Compound 1 was prepared by heating a mixture of basic
copper carbonate and H3cpida in water under steam bath
conditions, while compound 2 was synthesized by treating
Zn(NO3)2·6H2O with H3cpida in KOH/CH3OH/H2O under
hydrothermal conditions (Scheme 1Scheme 1). The pres-
ence of the characteristic band at 1703 cmϪ1 for compound
2 indicates that the deprotonation of H3cpida ligand is in-
complete, which is consistent with the crystal structure of 2.
Description of Crystal Structures
[a]
Department of Chemistry, University of Science and
Technology of China,
[Cu3(cpida)2(H2O)4]n·4nH2O (1)
Hefei 230026, P. R. China
Fax: (internat.) ϩ 86-551-363-1760
E-mail: zwang3@ustc.edu.cn
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
The polymeric structure of 1 was confirmed by an X-ray
single-crystal structure determination. The trinuclear entity
of compound 1 with the atomic labelling scheme is shown
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323
DOI: 10.1002/ejic.200400218
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4317

G.-P. Yong, Z. Y. Wang, Y. Cui
FULL PAPER
Scheme 1. Preparation of H3cpida and complexes 1 and 2
in Figure 1a. The two terminal CuII atoms (Cu1 and Cu1a)
adopt a JahnϪTeller-distorted octahedral coordination en-
vironment, resulting in a longer axial Cu1ϪO6 bond
˚
[2.344(2) A] from the coordinated water molecule and
3Ϫ
˚
Cu1ϪN1 bond [2.496(2) A] from the cpida ligand. The
equatorial plane is defined by four oxygen atoms, which
come from the bridging monodentate (O1), the monodent-
ate (O3) and the bridging bidentate (O7a) carboxylate
groups of two deprotonated cpida3Ϫ ligands, and the coor-
dinated water molecule (O5). The bond lengths Cu1ϪO are
˚
in the range 1.947(2)Ϫ1.978(2) A (Table 1). The central Cu2
atom presents a JahnϪTeller octahedral environment, re-
˚
sulting in very long axial Cu2ϪO6 bonds [2.608(2) A] to
the coordinated water molecule. The equatorial plane ge-
ometry is formed from the O1, O1a, O8 and O8a atoms of
the bridging monodentate and bidentate carboxylate groups
of four cpida3Ϫ ligands [Cu2ϪO ϭ 1.916(2) and 1.958 (2)
˚
A].
The adjacent CuII centres are bridged by one oxygen
atom of the monodentate carboxylate group and two oxy-
gen atoms of the bidentate carboxylate groups of two
cpida3Ϫ ligands, leading to a linear trinuclear CuII SBU
(Figure 1a). The three CuII atoms are arranged in a strictly
linear fashion (Cu1ϪCu2ϪCu1a ϭ 180°) with Cu2 at the
inversion centre; the distance between Cu1 and Cu2 is 3.232
Figure 1. a) ORTEP diagram of the coordination environment
around the linear trinuclear CuII unit in 1; thermal ellipsoids are
drawn at the 50% probability level; all hydrogen atoms are omitted
for clarity; symmetry code: a: Ϫx, Ϫy, Ϫz; b) 1D molecular-box
chain of 1 along the c axis; the black spheres represent copper
atoms
˚
A. Complex 1 is a rare example of a polynuclear metal clus-
ter bridged by carboxylate groups from only one kind of bridged compounds containing µ-hydroxo, µ-carboxylato,
ligand (cpida3Ϫ). To the best of our knowledge, only a lim- µ-acetato, etc.
ited number of linear trinuclear CuII compounds have been
Compound 1 possesses a 1D chain structure constructed
reported,[11Ϫ13] and few metal-organic coordination frame- from linear trinuclear Cu3 SBUs. Interestingly, four CuII
works containing a linear trinuclear CuII unit have been atoms of two Cu3 SBUs are linked by two cpida3Ϫ spacers
documented.[14] It is worth noting that 1 is the first linear in a head-to-tail mode leading to a parallelogram-shaped
trinuclear CuII compound in which the three CuII centres molecular box, as shown in Figure 1b. In each molecular
are linked by µ-carboxylato groups of only one type of li- box there are offset πϪπ stacking interactions between two
gand (cpida3Ϫ); other reported examples[11Ϫ14] are mixed- cpida3Ϫ aromatic rings (centroid···centroid ϭ 4.32 A). Each
˚
4318
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323

Copper() and Zinc() Coordination Polymers with a New Bridging Chelating Ligand
FULL PAPER
˚
[Zn(Hcpida)]n·nH2O (2)
Table 1. Selected bond lengths [A] and angles [°] for complexes 1
and 2
The asymmetric unit of 2 consists of one ZnII atom, one
Hcpida2Ϫ ligand and one guest water molecule. Each ZnII
centre is coordinated by two oxygen atoms (O1A, O4B)
from the bridging bidentate carboxylate groups of two
Hcpida2Ϫ ligands, and two oxygen atoms (O2, O3) from
one chelating bidentate Hcpida2Ϫ ligand, leading to a dis-
torted tetrahedral coordination geometry (Figure 3). The
1
2
Cu(1)ϪO(1)
Cu(1)ϪO(3)
Cu(1)ϪO(5)
Cu(1)ϪO(6)
Cu(1)ϪO(7a)
Cu(2)ϪO(1)
Cu(2)ϪO(1a)
Cu(2)ϪO(8)
Cu(2)ϪO(8a)
O(1)ϪCu(1)ϪO(3)
O(1)ϪCu(1)ϪO(5) 177.87(9) O(1A)ϪZn(1)ϪO(3) 143.5(2)
O(1)ϪCu(1)ϪO(6) 81.37(9) O(1A)ϪZn(1)ϪO(4B) 104.0(2)
O(1)ϪCu(1)ϪO(7a) 92.67(9) O(2)ϪZn(1)ϪO(3)
O(3)ϪCu(1)ϪO(5)
O(3)ϪCu(1)ϪO(6)
O(3)ϪCu(1)ϪO(7a) 171.45(9) O(1A)ϪZn(1)ϪN(1)
O(5)ϪCu(1)ϪO(6) 100.67(10) O(2)ϪZn(1)ϪN(1)
O(5)ϪCu(1)ϪO(7a) 88.03(10) O(3)ϪZn(1)ϪN(1)
O(6)ϪCu(1)ϪO(7a) 87.86(9) O(4B)ϪZn(1)ϪN(1) 165.3(2)
O(1)ϪCu(2)ϪO(1a) 180.00(14)
O(1)ϪCu(2)ϪO(8) 91.32(9)
O(1)ϪCu(2)ϪO(8a) 88.68(9)
1.978(2) Zn(1)ϪO(1A)
1.973(2) Zn(1)ϪO(2)
1.952(2) Zn(1)ϪO(3)
2.344(2) Zn(1)ϪO(4B)
1.947(2) Zn(1)ϪN(1)
1.958(2)
1.958(5)
1.983(5)
1.996(6)
2.002(5)
2.399(6)
˚
˚
ZnϪO bond lengths vary from 1.958(5) A to 2.002(5) A.
The bond angles around the ZnII centre range from 90.8(2)°
to 143.5(2)°. There is an unusual structural feature around
the ZnII centre: the ZnII centre has four nearest-neighboring
1.958(2)
1.916(2)
1.916(2)
93.14(8) O(1A)ϪZn(1)ϪO(2) 100.7(2)
˚
oxygen atoms [d(ZnϪO) Ͻ 2.002 A] in an approximately
tetrahedral arrangement, although the O1AϪZn1ϪO3
bond angle [143.5(2)°] is particularly obtuse. There is one
nitrogen atom associated with the Zn atom [d(ZnϪN) ϭ
110.0(2)
98.5(2)
90.8(2)
90.7(2)
79.1(2)
76.6(2)
85.94(10) O(2)ϪZn(1)ϪO(4B)
99.20(9) O(3)ϪZn(1)ϪO(4B)
˚
2.399 A], which does not constitute a ‘‘bond’’ in any real
sense. This association may be considered as a weak interac-
tion.[16] The geometry at the Zn centre can be visualized
as a mono-capped tetrahedron (Figure 3).[17] Because the
˚
Zn1ϪN1 bond (2.399 A) is much longer than the Zn1ϪO4
˚
bond (2.002 A), the ZnO4N unit should not be described
O(8)ϪCu(2)ϪO(1a) 88.68(9)
O(8)ϪCu(2)ϪO(8a) 180.0(2)
O(8a)ϪCu(2)ϪO(1a) 91.32(9)
as distorted trigonal-bipyramidal but as mono-capped
tetrahedral. On the other hand, the Zn atom is displaced
off-center by 0.317 A, when the associated nitrogen atom is
˚
considered. These results support the validity of regarding
this geometry as mono-capped tetrahedral.
parallelogram-shaped molecular box is then linked together
by the bridging bidentate carboxylate groups, which results
in the formation of a 1D molecular box coordination poly-
mer. It is notable that the 1D molecular box chains propa-
gate into 2D layers by an AA stacking pattern[15] in the bc
plane, as shown in Figure 2.
Figure 3. ORTEP diagram of the coordination environment around
the ZnII centre in 2; thermal ellipsoids are drawn at the 50% prob-
ability level; all hydrogen atoms are omitted for clarity; symmetry
code: A: x, Ϫy Ϫ 1/2, z Ϫ 1/2; B: Ϫx, y ϩ 1/2, Ϫz ϩ 1/2
The coordinated H3cpida ligand has an unchelated car-
˚
boxylic group. The CϪO bond [C11ϪO6 ϭ 1.344(10) A]
˚
is much longer than CϪO [C11ϪO5 ϭ 1.190(9) A] in the
carboxylic group, so C11ϪO5 can be assigned as the double
bond and C11ϪO6 as the single bond. This shows that de-
protonation of the H3cpida ligand is incomplete.
Figure 2. A view of the 2D layer of 1 down the a axis, showing the
AA stacking pattern of the 1D molecular box chains
One guest water molecule (O9) forms a hydrogen bond
with a coordinated water molecule (O9···O5 ϭ 2.695A), and work. The Zn1 centre is connected to four adjacent Zn
The crystal structure of 2 consists of an infinite 2D net-
˚
another guest water molecule (O10) forms hydrogen bonds centres through the bridging bidentate carboxylate groups
with the coordinated water molecule (O10···O5 ϭ 2.576A) of Hcpida2Ϫ ligands leading to a Zn4(Hcpida)4 unit, which
˚
and the noncoordinated carboxylate oxygen atom further extends into a 2D polymeric network with alternate
˚
(O10···O2 ϭ 2.725A).
large and small pseudo-square grid motifs in the bc plane
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4319

G.-P. Yong, Z. Y. Wang, Y. Cui
FULL PAPER
Figure 5. A topological illustration of the alternate large and small
grids of compound 2
dicular to the bc plane and parallel to the a axis (Figure 4c).
˚
Each alternate open channel is approximately 4.9 ϫ 5.7 A.
The guest water molecules occupy the open channels re-
sulting in the formation of the water columns along the a
direction.[18] It should be noted that in the crystal packing
there are offset πϪπ stacking interactions between two
Hcpida2Ϫ aromatic rings (centroid···centroid ϭ 4.10 A), as
˚
shown in Figure 6. The guest water molecule (O7) forms
hydrogen bonds with the coordinated carboxylate oxygen
˚
˚
atoms (O7···O1 ϭ 2.850 A; O7···O4 ϭ 2.961 A) and the
noncoordinated carboxylate oxygen atom (O7···O6 ϭ
2.680 A).
˚
Figure 4. a) The 2D network of 2 as viewed down the a axis, show-
ing alternate large and small pseudo-square grids (phenyl rings
omitted for clarity); b) a view of the 2D wave-like layer of 2 down
the c axis, showing the AA stacking pattern between the layers; c)
a space-filling diagram showing alternate open and closed channels
created perpendicularly to the bc plane; the alternate open channels
are occupied by the guest water molecules, which have been omitted
for clarity
(Figure 4a). In each large pseudo-square grid, the ZnϪZn
˚
separations are 4.90 and 5.20 A, while the ZnϪZnϪZn
angles are 80.73° and 99.27°. Each acetate group of the
Hcpida2Ϫ ligand adopts a bidentate bridging mode to con-
nect two Zn centres. Four Zn centres are connected together
by µ2-acetato groups to form a 2D grid network. However, Figure 6. The 3D structure of 2 as viewed down the b axis, showing
the offset πϪπ stacking interactions
according to the flexibility of the iminodiacetate groups of
the Hcpida2Ϫ ligand, compound 2 does not adopt one kind
of grid but alternate large and small grid motifs, as shown
in Figure 5. The wave-like nature of the 2D layers of 2 can
Removal of the Guest Water Molecules: TGA and PXRD
be clearly shown with a view of 2 down the c axis (Fig-
Studies
ure 4b). Interestingly, the 2D layers in 2 adopt an AA stack-
ing pattern in the ab plane, and the convex phenylcarboxylic
The X-ray single-crystal structures clearly indicate that
groups of Hcpida2Ϫ in one layer sit above or below the compound 2 possesses alternate open channels along the a
small grids of the adjacent layers along the a direction (Fig- axis, and we became intrigued by the possibility of generat-
ure 4b). Thus, compound 2 possesses alternate open (large ing a cavity by removing the guest water molecules. The
grids) and closed (small grids) channels that are perpen- TGA curve of compound 1 exhibits a continuous weight
4320
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323

Copper() and Zinc() Coordination Polymers with a New Bridging Chelating Ligand
FULL PAPER
This emission arises from ligand-to-metal charge transfer
(LMCT).[20] TGA indicated that 2 is thermally stable up to
340 °C. Thus, compound 2 may be a good candidate for
highly thermally stable and solvent-resistant photoactive
material because it is almost insoluble in common polar
and nonpolar solvents.[4a] Compound 2 may also have po-
tential as a porous material after removing the guest water
molecules.
Figure 7. TGA curves for 1 (a) and 2 (b)
loss (curve a in Figure 7): the loss of the guest water mol-
ecules is accompanied by the loss of the coordinated water
molecules, and the loss of the coordinated water molecules
is accompanied by the loss of the ligands. As a result, it is
difficult to give exact weight losses as a percentage for each
weight-loss step in the TGA curve. The removal of the guest
water molecules from 1 results in the collapse of the frame-
work structure (see Supporting Information). The TGA
curve of compound 2 exhibits an initial weight loss at an
onset temperature of 120 °C (5.43%), corresponding to the
removal of the guest water molecule (calcd. 5.38%). The
second weight loss occurs between 340 and 480 °C (69.23%)
and corresponds to the release of the Hcpida2Ϫ ligand
(curve b in Figure 7). The remaining weight of 25.34%
corresponds to the percentage of ZnO (calcd. 24.32%). Al-
though the hydrogen bonds increase the difficulty of remov-
ing the guest water molecule (O7) from 2,[19] the framework
structure of the dehydrated sample is simlar to that of com-
pound 2 in terms of their powder X-ray diffraction (PXRD)
patterns (see Supporting Information). The rehydrated
sample also exhibits a similar PXRD pattern to compound
2 (Supporting Information). In particular, the existence of
the strongest peak at a 2θ value of 6.56° in the three PXRD
patterns shows that the layer framework of 2 does not
change upon dehydration and rehydration. Therefore, com-
pound 2 not only maintains its 2D layer framework after
Figure 8. The emission spectra of the H3cpida ligand (a) and com-
pound 2 (b) in the solid state at room temperature
Conclusions
Two new metal-organic coordination polymers have been
synthesised. Compound 1 is a linear trinuclear CuII com-
pound in which the three CuII centres are linked only by
µ-carboxylato groups of the same ligand (cpida3Ϫ). A 1D
parallelogram-shaped molecular-box chain is constructed
from these unusual linear trinuclear CuII SBUs. Compound
2 possesses alternate open and closed channels and shows
strong photoluminescence, thus it may be a good candidate
for a photoactive or porous material.
Experimental Section
dehydration but the inclusion process is reversible to some General Remarks: All commercially available chemicals were of re-
agent grade and used as received without further purification. In-
frared spectra were recorded with a Bruker VECTOR-22 FT-IR
spectrophotometer as KBr pellets. 1H NMR spectra were measured
with an Avance AV400 NMR spectrometer at room temperature.
Powder X-ray diffraction (PXRD) patterns were obtained with an
MXPAHF rotating-anode X-ray diffractometer. The luminescence
spectra for the solid samples were recorded at room temperature
with a Hitachi 850 fluorescence spectrophotometer. Thermogravi-
metric analyses (TGA) were performed under air with a heating
rate of 10 °C·minϪ1 using a Shimadzu TGA-50H TG analyzer.
extent. This can be attributed to the absence of coordinated
water molecules in compound 2 and the higher decompo-
sition temperature (340 °C) of the Hcpida2Ϫ ligand.
Photoluminescence Properties of H3cpida and 2
The solid-state photoluminescence spectra of H3cpida
and compound 2 at room temperature are depicted in Fig-
ure 8; H3cpida exhibits a broad strong blue-fluorescent em-
ission around 422 nm upon excitation at 332 nm (curve a
in Figure 8). Interestingly, in the case of the metal-organic
polymer 2, a blue-shifted photoluminescence with the main
emission at 366 nm and with a shoulder at about 480 nm
N-(4-Carboxyphenyl)iminodiacetic Acid (H3cpida): A solution of
KOH (33.6 g, 0.6 mol) in water (100 mL) was added dropwise to a
solution of chloroacetic acid (28.4 g, 0.3 mol) in water (100 mL).
upon excitation at 313 nm is observed (curve b in Figure 8). p-Aminobenzoic acid (13.7 g, 0.1 mol) was slowly added to the re-
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323
www.eurjic.org  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4321

G.-P. Yong, Z. Y. Wang, Y. Cui
FULL PAPER
sulting alkaline solution, and the mixture was refluxed at 86 °C for
30 h. The reaction mixture was then cooled to room temperature
and acidified with HCl (6 ) until the desired acid precipitated as
a white solid (pH ഠ 2.5) (Scheme 1). This precipitate was collected
by filtration, washed with water and recrystallised from water
(yield: 32% based on p-aminobenzoic acid). IR (KBr): ν˜ ϭ 3458,
Table 1. CCDC-228511 (1) and -228512 (2) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
[or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-
033; E-mail: deposit@ccdc.cam.ac.uk].
2919, 1714, 1612, 1530, 1462, 1388, 1239, 1192, 975, 771, 692 cmϪ1
.
1H NMR (400 MHz, D2O, 25 °C): δ ϭ 7.84 (d, J ϭ 8.9 Hz, AABB,
2 H), 6.58 (d, J ϭ 8.9 Hz, AABB, 2 H), 4.23 (s, 4 H, CH2-COO)
ppm.
Acknowledgments
The authors gratefully acknowledge the financial support of the
National Natural Science Foundation of China (no. 50073021) and
the Foundation of the Education Department of Anhui Province
(2002kj330ZD).
[Cu3(cpida)2(H2O)4]n·4nH2O (1): This compound was prepared by
a solvent evaporation method. A mixture of basic copper carbonate
(0.111 g, 0.5 mmol) and H3cpida (0.25 g, 1.0 mmol) in 15 mL of
water was heated in a steam bath for 1 h, and then filtered. Meth-
anol (5 mL) was then added to the filtrate (Scheme 1). Blue single
crystals suitable for X-ray analysis were obtained by slow evapo-
ration of the solvent from the filtrate at room temperature (yield:
72% based on Cu). IR (KBr): ν˜ ϭ 3418, 2919, 1645, 1605, 1538,
[1] [1a]
M. Eddaoudi, D. B. Moler, H. L. Li, B. Chen, T. Reineke,
M. O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319Ϫ330.
[1b]
S. R. Batten, R. Robson, Angew. Chem. Int. Ed. 1998, 37,
[1c]
1460Ϫ1494.
P. J. Hagrmann, D. Hagrman, J. Zubieta, An-
gew. Chem. Int. Ed. 1999, 38, 2638Ϫ2684. [1d] M. O’Keeffe, M.
1412, 1260, 1217, 1170, 968, 925, 839, 778, 698, 643, 511 cmϪ1
.
Eddaoudi, H. L. Li, T. Reineke, O. M. Yaghi, J. Solid State
[1e]
[Zn(Hcpida)]n·nH2O (2): This compound was synthesized hydro-
thermally in a thick-walled Pyrex tube containing Zn(NO3)2·6H2O,
H3cpida, KOH, methanol and H2O in a molar ratio of 3:2:1:78:222
under autogenous pressure. The tube was cooled in liquid N2,
sealed under vacuum, and placed inside an oven at 120 °C for 2
d (Scheme 1). The resulting colourless crystals were collected and
washed with ethanol (yield: 58% based on Zn). IR (KBr): ν˜ ϭ 3491,
2977, 1703, 1573, 1518, 1460, 1412, 1352, 1308, 1262, 1197, 1146,
Chem. 2000, 152, 3Ϫ20.
Trans. 2000, 3735Ϫ3744.
R. Robson, J. Chem. Soc., Dalton
B. Moulton, M. J. Zaworotko,
[1f]
Chem. Rev. 2001, 101, 1629Ϫ1658.
[2] [2a]
J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon, K.
[2b]
Kim, Nature 2000, 404, 982Ϫ986.
O. Kahn, C. Martinez,
O. R. Evans, R.-G. Xiong, Z.-Y.
Wang, G.-K. Wong, W.-B. Lin, Angew. Chem. Int. Ed. 1999,
[2c]
Science 1998, 279, 44Ϫ48.
[2d]
38, 536Ϫ538.
W.-B. Lin, O. R. Evans, R.-G. Xiong, Z.-Y.
Wang, J. Am. Chem. Soc. 1998, 120, 13272Ϫ13273.
1122, 1016, 923, 851, 781, 755, 731, 699, 648, 585, 508 cmϪ1
.
[3] [3a]
H. L. Li, M. Eddaoudi, M. O’Keeffe, O. M. Yaghi, Nature
[3b]
1999, 402, 276Ϫ279.
S. S.-Y. Chui, S. M.-F. Lo, J. P. H.
X-ray Single-Crystal Structure Determination: Crystallographic
data for 1 and 2 were collected at 173 K for 1 and 293 K for 2 with
a Siemens Smart CCD diffractometer with Mo-Kα radiation (λ ϭ
Charmant, A. G. Orpen, I. D. Williams, Science 1999, 283,
1148Ϫ1150.
[4] [4a]
J.-C. Dai, X.-T. Wu, Z.-Y. Fu, S.-M. Hu, W.-X. Du, C.-P.
˚
0.71073 A). The structures were solved by direct methods using
Cui, L.-M. Wu, H.-H. Zhang, R.-Q. Sun, Chem. Commun.
[4b]
SHELXS-97[21] and refined by full-matrix least-squares method
against F2 (SHELXL-97).[22] All non-hydrogen atoms were refined
anisotropically. Carbon-bound hydrogen atoms were placed in geo-
metrically calculated positions; oxygen-bound hydrogen atoms
were located in the difference Fourier map and kept fixed in that
position. The crystallographic data for 1 and 2 are listed in Table 2;
selected bond lengths and angles for 1 and 2 are presented in
2002, 12Ϫ13.
J.-C. Dai, X.-T. Wu, Z.-Y. Fu, C.-P. Cui, S.-
M. Hu, W.-X. Du, L.-M. Wu, H.-H. Zhang, R.-Q. Sun, Inorg.
Chem. 2002, 41, 1391Ϫ1396.
[5]
[5a] C. J. Kepert, T. J. Prior, M. J. Rosseinsky, J. Am. Chem. Soc.
[5b]
2000, 122, 5158Ϫ5168.
J. W. Wo, K. S. Min, M. P. Suh,
[5c]
Inorg. Chem. 2002, 41, 2151Ϫ2157.
M. Guo, L. Zhang, D.-Z. Liao, J. Ribas, Chem. Commun. 2002,
M. Du, X.-H. Bu, Y.-
[5d]
´
C. Ruiz-Perez, J. Sanchiz, M. H. Molina, F.
1478Ϫ1479.
Lloret, M. Julve, Inorg. Chem. 2000, 39, 1363Ϫ1370.
[6]
[7]
[6a] O. M. Yaghi, C. E. Davis, G. Li, H. L. Li, J. Am. Chem. Soc.
Table 2. Crystal data and structure refinement for complexes 1
and 2
[6b]
1997, 119, 2861Ϫ2868.
O. Kristiansson, L.-E. Tergenius, J.
Chem. Soc., Dalton Trans. 2001, 1415Ϫ1420. [6c] M. Eddaoudi,
J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O. M.
Yaghi, Science 2002, 295, 469Ϫ472.
1
2
[7a] E. Brunet, M. T. Alonso, O. Juanes, O. Velasco, J. C. Rodri-
[7b]
Empirical formula
Formula mass
Temperature [K]
Crystal system
Space group
C22H32Cu3N2O20 C11H11NO7Zn
guez-Ubis, Tetrahedron 2001, 57, 3105Ϫ3116.
enbacher, R. Saf, R. Schitter, K. Hummel, Synthetic Met. 1999,
G. Schwarz-
835.12
173(2)
triclinic
334.56
293(2)
monoclinic
P21/c
101, 143Ϫ144.
[8] [8a]
M. Sirak, M. Mad’arova, J. Tatiersky, J. Marek, Eur. J. In-
org. Chem. 2003, 2075Ϫ2081.
J. C. G. Bunzli, Eur. J. Inorg. Chem. 2003, 1332Ϫ1339.
[8b]
¯
P1
D. Imbert, N. Fatin-Rouge,
[8c]
˚
a [A]
8.5094(17)
9.3206(19)
10.392(2)
92.274(4)
93.803(4)
112.850(4)
756.0(3)
1
13.900(3)
9.513(2)
9.375(2)
90
101.136(5)
90
1216.4(5)
4
2.041
S.
˚
b [A]
Ulvenlund, A. S. Georgopoulou, D. M. P. Mingos, I. Baxter,
˚
c [A]
S. E. Lawrence, A. J. P. White, D. J. Williams, J. Chem. Soc.,
[8d]
α [°]
β [°]
γ [°]
Dalton Trans. 1998, 1869Ϫ1878.
R. Ruloff, R. Richter, L.
Beyer, Z. Anorg. Allg. Chem. 1998, 624, 902Ϫ908.
S. Burnet, A. K. Hall, J. M. Harrowfield, G. A. Koutsantonis,
V. Sanford, D. Sauter, B. W. Skelton, A. H. White, Supramol.
Chem. 2003, 15, 291Ϫ312.
[9]
3
˚
V [A ]
Z
µ [mmϪ1
]
2.183
X.-M. Ouyang, D.-J. Liu, T. Okamura, H.-W. Bu, W.-Y. Sun,
W.-X. Tang, N. Ueyama, Dalton Trans. 2003, 1836Ϫ1845.
[10]
Reflections collected
Independent reflections (Rint
Observed reflections
R1, wR2 [I Ն 2σ(I)]
3991
3181 (0.0131)
2614
5090
1746 (0.0566)
1326
)
[11] [11a] G. A. van Albada, I. Mutikainen, U. Turpeinen, J. Reedijk,
[11b]
Eur. J. Inorg. Chem. 1998, 547Ϫ549.
G. A. van Albada, P.
0.0374, 0.0882
0.0634, 0.1481
J. van Koningsbruggen, I. Mutikainen, U. Turpeinen, J. Reed-
ijk, Eur. J. Inorg. Chem. 1999, 2269Ϫ2275.
4322
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323

Copper() and Zinc() Coordination Polymers with a New Bridging Chelating Ligand
FULL PAPER
[12] [12a]
[18]
[19]
´
´
M. H. W. Lam, Y.-Y. Tang, K.-M. Fung, X.-Z. You, W.-
R. Atencio, M. Chacon, T. Gonzalez, A. Bricefio, G. Agrifog-
lio, A. Sierraalta, Dalton Trans. 2004, 505Ϫ513.
D.-F. Sun, R. Cao, Y.-Q. Sun, W.-H. Bi, X.-J. Li, Y.-Q. Wang,
Q. Shi, X. Li, Inorg. Chem. 2003, 42, 7512Ϫ7518.
J. Tao, M.-L. Tong, J.-X. Shi, X.-M. Chen, S. Ng, Chem.
Commun. 2000, 2043Ϫ2044.
M. Vassrin, A. Gulino, E. Tondello, A. Vittadini, Inorg. Chem.
T. Wong, Chem. Commun. 1997, 957Ϫ958. [12b] T. C. Higgs, K.
Spartalian, C. J. O’Connor, B. F. Matzanke, C. J. Carrano, In-
org. Chem. 1998, 37, 2263Ϫ2272.
[20] [20a]
[13]
Y. F. Song, P. Gamez, O. Roubeau, M. Lutz, A. L. Spek, J.
[20b]
R. Bertoncello, M. Bettinelli,
Reedijk, Eur. J. Inorg. Chem. 2003, 2924Ϫ2928.
[14] [14a]
´
M.
L. Gutierrez, G. Alzuet, J. A. Real, J. Cano, J. Borras,
[20c]
1992, 31, 1558Ϫ1565.
J. Tao, J.-X. Shi, M.-L. Tong, X.-X.
[14b]
A. Castin˜eiras, Eur. J. Inorg. Chem. 2002, 2094Ϫ2102.
Zhang, X.-M. Chen, Inorg. Chem. 2001, 40, 6328Ϫ6330.
G. M. Sheldrick, SHELXS-97, Program for X-ray Crystal
Structure Solution, Göttingen University, Germany, 1997.
G. M. Sheldrick, SHELXL-97, Program for X-ray Crystal
Structure Refinement, Göttingen University, Germany, 1997.
Received March 19, 2004
´
´
´
´
Gonzalez-Alvarez, G. Alzuet, J. Borras, B. Macıas, A. Casti-
n˜eiras, Inorg. Chem. 2003, 42, 2992Ϫ2998.
W.-B. Lin, P. Ayyappan, Polyhedron 2003, 22, 3037Ϫ3042.
[21]
[22]
[15]
[16]
T. A. Bowden, H. L. Milton, A. M. Z. Slawin, P. Lightfoot,
Dalton Trans. 2003, 936Ϫ939.
[17]
M. G. Johnston, W. T. A Harrison, Inorg. Chem. 2001, 40,
6518Ϫ6520.
Early View Article
Published Online August 26, 2004
Eur. J. Inorg. Chem. 2004, 4317Ϫ4323
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4323