Polyhedron 25 (2006) 1215–1222

www.elsevier.com/locate/poly

Coordination polymers constructed from o-phthalic acid and

diamines: Syntheses and crystal structures of the
phthalate-imidazole complexes {[Cu(Pht)(Im)2] Æ 1.5H2O}n
and [Co(Pht)(Im)2]n and their application in oxidation catalysis
Svetlana G. Baca a,*, Manfred T. Reetz b, Richard Goddard b, Irina G. Filippova c,
Yurii A. Simonov c, Maria Gdaniec d, Nicolae Gerbeleu a
a
Institute of Chemistry, Moldova Academy of Sciences of RM, Academiei 3, MD-2028 Chisinau, R. Moldova
b
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim an der Ruhr, Germany
c
Institute of Applied Physics, Moldova Academy of Sciences of RM, Academiei 3, MD-2028 Chisinau, R. Moldova
d
Faculty of Chemistry, A. Mickiewicz University, 60-780 Poznan, Poland

Received 16 July 2005; accepted 2 September 2005

Available online 11 October 2005

Abstract

Two new copper(II) and cobalt(II) coordination polymers, {[Cu(Pht)(Im)2] Æ 1.5H2O}n (1) and [Co(Pht)(Im)2]n (2) (where
Pht2
= dianion of o-phthalic acid; Im = imidazole) have been synthesized and their crystal structures determined by X-ray crystallog-
raphy. The structures of 1 and 2 comprise, respectively, [Cu(Im)2] and [Co(Im)2] units linked by bridging 1,6-phthalate ions to form infi-
nite chains. Although there are two independent Cu atoms in the structure of 1, each copper(II) center adopts an approximately square
planar coordination mode with two O atoms from different phthalate ions and two N atoms of Im. In complex 2, cobalt(II) atoms are
tetrahedrally coordinated. Extended hydrogen bonding networks stabilize the three-dimensional structures in both complexes. Prelimin-
ary results show that 1 and 2 exhibit catalytic activity on the oxidation of cyclohexene using hydrogen peroxide as oxidant under aerobic
conditions at ambient temperature.

2005 Elsevier Ltd. All rights reserved.

Keywords: Copper(II) complex; Cobalt(II) complex; Phthalate compounds; Coordination polymers; Crystal structures; Catalysis

1. Introduction lability are also efficient catalysts in a vast range of chem-

Coordination polymers or hybrid inorganic–organic
materials composed of metal centers bridged by organic
connectors are currently under active investigation, and
for recent reviews see [1]. Much of the interest centers on
their potential applications such in gas adsorption, molec-
ular recognition, magnetism, and photochemistry. The
coordination polymers with moderate stability and high
*
Corresponding author. Tel.: +373 22 72 5490/73 9611; fax: +373 22 73
9954/73 9611.
E-mail address: sbaca_md@yahoo.com (S.G. Baca).
ical and biochemical processes [2].
Our investigations [3–10] into the synthesis of new coor-
dination polymers using dicarboxylic acid as the spacer as
well as other studies [11–48] show that o-phthalic acid
(H2Pht) is a useful building block for the creation of such
systems. H2Pht and its anions, HPht
and Pht2
can adopt
a wide variety of coordination modes with metal centers,
and the observed architecture is the result of a subtle inter-
play between steric hindrance resulting from the close
proximity of the two ortho-carboxylic groups and the ten-
dency of phthalates to form the greatest possible number
of metal–oxygen bonds upon complexation. So far 26 dif-
ferent coordination types have been observed in crystal

0277-5387/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2005.09.003
1216 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222

structures containing this ligand [7]. Of these the 1,6-bridg-
ing mode, which favors the formation of the coordination
polymers, is the most common. The phthalate ligand can
also take part in additional weak hydrogen bonding, which
stabilizes the polymeric structures by forming two- and
three-dimensional networks. We have shown that a suc-
cessful preparation of coordination polymers is based on
a suitable choice of combinations of the phthalate bridging
ligand and different amines, such as pyridine, imidazole
and its derivatives, 2,2 0 -bipyridine, and 1,10-phenanthro-
line, which act as terminal ligands. Depending on both
the nature of the amines and the stoichiometric ratio meta-
l:acid:amines, infinite linear [4], zigzag [5,6] or helical [8,10]
chains are formed.
Oxidation reactions have synthetic applications in both
the chemical and pharmaceutical industries. The catalytic
oxidation of alkenes has potentially important industrial
applications since the selective oxidation products serve
as starting materials for the production of many fine chem-
icals. Oxidation can be carried out with many different oxi-
dants, but from an economic point of view H2O2 is ideally
suitable. It is cheap, readily available and environmentally
benign. A large effort is thus currently in progress to try to
find active catalysts for the oxidation reactions using this
oxidant. Several families of catalysts are known, mainly
based on various transition-metal complexes as titanium,
vanadium, molybdenum, manganese, tungsten and rhe-
nium complexes [49]. The cobalt-catalyzed decomposition
of hydroperoxides has also been extensively studied [50],
but catalytic oxidation catalyzed by copper complexes is
comparatively rare. Recently, a series of reports have been
published showing that b-carbonylenolate, b-diketonate
and b-ketamidate copper(II) complexes [51,52] and
mixed-ligand salicylaldehyde copper(II) complex [53] can
be used for catalytic oxidation cyclohexene under Mukaiy-
ama
s conditions. Some copper-based catalysts have also
been reported to be active in the presence of H2O2 [54,55].
The present work reports the synthesis of two phthalate
based copper(II) and cobalt(II) coordination polymers
using imidazole (Im) as the amine, {[Cu(Pht)(Im)2] Æ
1.5H2O}n (1) and [Co(Pht)(Im)2]n (2), their crystal structures
and presents a preliminary investigation into the catalytic
activity of 1 and 2 towards the oxidation of cyclohexene
using hydrogen peroxide as oxidant under aerobic conditions.
2. Experimental
2.1. Materials and methods
All the starting materials were reagent grade and used as
purchased. Hydrogen peroxide (30% aqueous solution) was
used as received from Acros. The infrared spectra were re-
corded on a Perkin–Elmer Spectrum One spectrometer
using KBr pellets in the region 4000–400 cm
1. Gas chro-
matographic analyses were carried out with a HP 5890
instrument on a RTX-5 column 30 m · 0.25 mm · 0.5 lm
fitted with a flame ionization detector, and hydrogen gas
pressure was 0.4 bar.

Table 1
Crystal data and structure refinement
1 2
Empirical formula C28H30Cu2N8O11 C14H12CoN4O4
Formula weight 781.68 359.21
Temperature (K) 100 293(2)
Wavelength (Å) 0.71073 0.71073
Crystal size (mm) 0.38 · 0.11 · 0.02 0.3 · 0.2 · 0.5
Crystal system orthorhombic monoclinic
Space group Pbca (No. 61) Pn (No. 7)
a (Å) 19.6319(3) 8.399(2)
b (Å) 13.6365(3) 9.978(2)
c (Å) 23.4334(4) 10.011(2)
a () 90 90
b () 90 104.43(3)
c () 90 90
V (Å3) 6273.4(2) 812.5(3)
Z 8 2
Dc (g cm
3) 1.655 1.468
l (mm
1) 1.430 1.080
F(0 0 0) 3200 366
h Range for data collection () 4.59–32.56 3.65–29.18
Index ranges
23 6 h 6 29;
10 6 k 6 20;
31 6 l 6 35
10 6 h 6 11;
13 6 k 6 13;
13 6 l 6 13
Reflections collected 37 115 4912
Reflections unique (Rint) 11 244 (0.1058) 2425 (0.0206)
Completeness to hmax 98.6 90.5
Data/restraints/parameters 11 244/0/452 2425/2/208
Final R indices [I > 2r(I)] R1 = 0.0620, wR2 = 0.1176 R1 = 0.0281, wR2 = 0.0740
R indices (all data) R1 = 0.1305, wR2 = 0.1408 R1 = 0.0315, wR2 = 0.0787
Goodness-of-fit on F2 1.008 0.939
Largest difference peak and hole (e Å
3) 0.662 and
0.654 0.645 and
0.377
 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222 1217

2.2. Synthesis of complexes SAINT program from Bruker-Nonius (Madison, USA) and
KUMA diffraction (Wroclaw, Poland) software. Crystal
2.2.1. Synthesis of {[Cu(Pht)(Im)2] Æ 1.5H2O}n (1) data, details of data collections and refinement for 1 and
Method A. To a hot suspension of o-phthalic acid 2 are given in Table 1. The structures were solved by direct
(0.66 g, 4 mmol) and CuCO3 Æ Cu(OH)2 (0.44 g, 2 mmol) methods (SHELXS-97 [56]) and refined on F2 (SHELXL-97 [57])
in 40 ml H2O was added Im (0.55 g, 8 mmol). The resulting using anisotropic displacement parameters for non-H
blue mixture was stirred and refluxed for 30 min and then atoms. Except for the solute water molecules in 1, H atoms
filtered. The filtrate was allowed to stand at room temper- were located from difference electron density syntheses and
ature. Blue crystals, suitable for X-ray analysis, were fil- refined using a riding model. Selected bond distances and
tered off the next day, washed with water, ethanol and angles are listed in Table 2.
acetone, and dried in air. Yield: 0.87 g (56%). Anal. Calc.
for C28H26Cu2O11N8: C, 43.02; H, 3.87; N, 14.33; Cu, 3. Results and discussion
16.26. Found: C, 43.09; H, 3.71; N, 14.08; Cu, 16.20%.
IR data (KBr, cm
1): 3479m, 3380m, 3137s, 3067m, 3.1. Crystal structures
2959m, 2871m, 1616vs, 1587vs, 1570vs, 1539sh, 1506sh,
1485m, 1443m, 1385vs, 1370vs, 1330m, 1263w, 1182w, 3.1.1. The structure of {[Cu(Pht)(Im)2] Æ 1.5H2O}n (1)
1148w, 1071s, 955w, 859m, 829m, 750s, 719m, 705m. The Fig. 1 shows a view of crystallographically independent
compound is insoluble in alcohol, acetone, acetonitrile, structure fragment of complex 1. The crystal structure of 1
chloroform, and poorly soluble in water. is characterized by [Cu(Im)2] entities linked into infinited
Method B. To a hot solution of o-phthalic acid (0.83 g, chains by bridging phthalate anions. The observed chain
5 mmol) and Im (0.69 g, 10 mmol) in 20 ml H2O was added structure (Fig. 2) is not unusual and has been found in
Cu(CH3COO)2 Æ H2O (0.99 g, 5 mmol). The resulting blue the crystal structures of the catenates (l2-o-phthalato)-
solution was heated for 10 min and allowed to stand at bis(pyridine)-copper(II) [16], ethylenediamine-(l2-o-phtha-
room temperature. Blue crystals formed after 1–2 days.
They were filtered off, washed with water, ethanol and ace-
Table 2
tone, and dried in air. Yield: 0.82 g (42%). It was identified Selected bond distances (Å) and bond angles () for compounds 1 and 2
by comparing its IR spectrum with the crystallographically
1
characterized precipitate from Method A, and elemental Cu(1)–N(1) 1.956(3)
analysis. Anal. Found for the title compound: C, 42.69; Cu(1)–N(3) 1.980(2)
H, 3.77; N, 13.80; Cu, 15.72%. Cu(2)–O(4) 1.971(2)
Cu(2)–O(7)* 1.972(2)
Cu(1)–O(5) 1.965(2)
2.2.2. Synthesis of [Co(Pht)(Im)2]n (2)
Cu(1)–O(1) 1.999(2)
To a hot solution of H2Pht (0.83 g, 5 mmol) and Im Cu(2)–N(5) 1.972(3)
(0.69 g, 10 mmol) in water (15 ml) Co(O2CMe)2 Æ 4H2O Cu(2)–N(7) 1.978(3)
(1.25 g, 5 mmol) was added. The resulting mixture was stir- N(1)–Cu(1)–O(5) 90.50(9)
red and heated for 20 min. The lilac precipitate so formed O(5)–Cu(1)–N(3) 91.31(9)
was filtered off from hot solution, washed with hot water, O(5)–Cu(1)–O(1) 167.34(9)
ethanol and acetone and dried in air. Yield: 0.84 g O(4)–Cu(2)–N(5) 89.38(10)
(46.8%). Anal. Calc. for C14H12CoN4O4: C, 46.81; H, N(5)–Cu(2)–O(7)* 91.64(10)
N(5)–Cu(2)–N(7) 168.69(12)
3.37; N, 15.60; Co, 16.41. Found: C, 46.72; H, 3.32; N, N(1)–Cu(1)–N(3) 171.56(11)
15.49; Co, 16.33%. IR data (KBr, cm
1): 3137s, 3062m, N(1)–Cu(1)–O(1) 89.32(9)
2970m, 2880m, 1612s, 1589vs, 1579sh, 1486m, 1460m, N(3)–Cu(1)–O(1) 90.72(9)
1444m, 1394s, 1373vs, 1329m, 1267m, 1144m, 1107m, O(4)–Cu(2)–O(7)* 176.25(10)
1075vs, 957m, 914w, 840m, 752s, 702m, 656vs, 620m, O(4)–Cu(2)–N(7) 91.11(10)
O(7)*–Cu(2)–N(7) 88.60(10)
606w, 573w, 482m. Single crystals suitable for diffraction
studies were obtained by recrystallization of 2 from hot 2
aqueous solution. Co(1)–O(4) 1.952(2)
Co(1)–N(1A) 2.002(3)
2.3. Crystal structure determinations Co(1)–O(1)** 1.980(2)
Co(1)–N(1B) 2.001(2)

Experimental data were collected on Bruker-Nonius O(4)–Co(1)–O(1)** 92.8(1)

O(1)*–Co(1)–N(1B) 116.5(1)
KappaCCD and KUMA KM4CCD-j-axis diffractometers
O(1)*–Co(1)–N(1A) 108.4(1)
using graphite monochromated Mo Ka radiation at 100 K O(4)–Co(1)–N(1B) 108.9(1)
for 1 and 293 K for2. The crystals were located 40 mm (1)/ O(4)–Co(1)–N(1A) 121.7(1)
60 mm (2) from the CCD camera. 446/444 Frames were N(1B)–Co(1)–N(1A) 108.3(1)
collected in 2/4 runs with a 0.5/0.5 scan width and Symmetry transformations used to generate equivalent atoms: * x,
y + 3/2,
150 s/10 s per frame. The data were processed using the z + 1/2; ** x + 1/2,
y + 1, z + 1/2.
1218 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222

Fig. 1. Crystallographically independent structure fragment in compound 1. Hydrogen atoms are omitted for clarity and long contacts Cu(1)–O and
Cu(2)–O are indicated by double dotted lines. Atomic displacement ellipsoids are shown at the 50% probability level.

Fig. 2. The fragments of two polymeric chains in compound 1. Hydrogen atoms are omitted for clarity. Hydrogen bonds are indicated by dotted lines and
long contacts Cu–O are indicated by double dotted lines.

lato)-copper(II) [17], aqua-(1,10-phenanthroline)-(l2-o- imately square-planar N2O2 coordination. The O–Cu–O

phthalato)-copper(II) [18], (l2-o-phthalato)-bis(piperidine)-
copper(II) [20], bis(l2-o-phthalato)-aqua-tetrakis(4-meth-
ylpyridine)-di-copper(II) [2], diammine-(l2-o-phthalato)-
copper(II) [8], and (1-methylimidazole)-(l2-o-phthalato)-
copper(II) [6] and aqua-(4-methylimidazole)-(l2-o-phtha-
lato)-copper(II) [7] among others. The mode of attachment
of the phthalate dianion to the metal is not always the
same. In some cases, the carboxylic acid groups are at-
tached by both oxygen atoms and in others by one oxygen
atom.
There are two crystallographically independent Cu(II)
centers within chains and both Cu(II) atoms have approx-
angles range from 167.3(1) (O(1)–Cu(1)–O(5)) to
176.3(1) (O(4)–Cu(2)–O(7)) and the N–Cu–N angles vary
from 168.7(1) (N(5)–Cu(2)–N(7)) to 171.6(1) (N(1)–
Cu(1)–N(3)). The different arrangement of the C@O bonds
of the carboxylic acid groups relative to the coordination
planes of the two independent Cu atoms indicate that the
chain is relatively flexible and successive Cu  Cu distances
in the chain are 6.045(1) and 6.468(1) Å. Whereas the Cu–
X distances vary significantly for Cu(1) [Cu(1)–N(1)
1.956(3), Cu(1)–N(3) 1.980(2), Cu(1)–O(1) 1.999(2),
Cu(1)–O(5) 1.965(2) Å], this is not the case for Cu(2)
[Cu(2)–N(5) 1.972(3), Cu(2)–N(7) 1.978(3) Å, Cu(2)–O(4)
 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222
1.971(2), Cu(2)–O(7)* 1.972(2) Å]. Note, the Cu(1) and
Cu(2) atoms additionally form two long contacts: Cu(1)–
O(2) 2.559(2), Cu(1)–O(6) 2.894(2) Å with uncoordinated
oxygen atoms of both carboxylic groups; Cu(2)–O(1w) is
2.644 and Cu(2)–O(3) is 2.861 Å. Consequently, the coordi-
nation of both Cu atoms can be described as 4 + 1 + 1.
All of the four independent imidazole ligands in 1 are in-
volved in N–H  O hydrogen bonding interactions, of
which only one is intramolecular. Thus, N(6) forms an
intramolecular H bonding interaction with the free car-
bonyl O atom of a phthalate ligand further along the chain.
The distance N(6)  O(2) is 2.793(4) Å and this is compara-
ble to the distance N(8)  O(2w) (2.787(4) Å) between the
trans imidazole group N–H group and a solute water mol-
ecule. There is also an additional intermolecular contact
between N(2) and the water molecule O(1w) of
3.040(4) Å such that N(2) forms a bifurcated hydrogen
bond to O(7) and O(1w). The remaining two independent
imidazole groups, both of which are attached to Cu(1),
form direct interchain N–H  O–Cu hydrogen bonds to
the O atoms of the phthalate groups bonded to the Cu
atoms in neighboring chains. The corresponding inter-
atomic distances are N(4)  O(4) = 2.785(3) and
N(2)  O(7) = 3.109(4) Å. This extended hydrogen bond-
ing network stabilizes a 3D structure in complexes 1.
Fig. 2 presents a fragment of packing arrangement in 1.
3.1.2. The structure of [Co(Pht)(Im)2]n (2)
The structure of 2 comprises [Co(Im)2] units linked into
zigzag polymeric chains by bridging phthalate anions.
Fig. 3 shows a fragment of the chain in compound 2, to-
gether with the atomic labeling scheme. The crystals are
isostructural with the analogous Zn(II) complex [6]. Each
Co atom adopts a tetrahedral N2O2 geometry, being
coordinated by a pair of imidazole ligands [Co(1)–
N(1a) = 2.002(3) and Co(1)–N(1b) = 2.001(2) Å] and a
pair of monodentate carboxylate groups [Co(1)–
Fig. 3. Polymeric chain in compound 2 with numbering scheme. The
atomic displacement ellipsoids are drawn at the 50% probability level.
1219
O(1)* = 1.980(2) and Co(1)–O(4) = 1.952(2) Å]. The bond
angles at Co(1) atom range from 92.8(1) to 121.7(1)
(Table 2). As expected, distances and angles in coordina-
tion polyhedron agree well with those in [Zn(Pht)(Im)2]n
[6]. The nearest Co  Co distances in the chain are at
6.017(2) Å. The dihedral angles between the planes
through the carboxylate groups [O(1)C(11)O(2) and
O(3)C(22)O(4)] and the aromatic ring are 61.9(2) and
33.7(2), respectively. For Pht ligand, the C–C bonds
within the aromatic ring range from 1.373(5) to
1.404(4) Å and are similar to those in complex 1 and other
Cu(II) phthalate complexes [3,7,8]. The bond distances
and angles of the imidazole molecules also fall in the range
of values found in other complexes, containing the coordi-
nated imidazole [58,59].
The chains lie parallel along the [1 0 1] direction. The
N(3b)–H(3b)  O(2) [x, y + 1, z] = 2.754(4) Å hydrogen
bonds connect the chains into layers (Fig. 4) and N(3a)–
H(3a)  O(1) [x + 1, y, z] = 2.812(4) Å interactions com-
bine neighboring layers into a 3D network. Interestingly,
in contrast to 1, the crystal structure of 2 contains no solute
water, even though the crystals of 2 were grown from hot
aqueous solution.
3.2. Spectroscopic properties
IR spectra of compounds 1 and 2 showed absorptions
due to N–H bond stretching of imidazole ligands and C–
H bonds of aromatic rings in the range 3380–2871 cm
1.
Strong bands in the 1616–1570 and 1385–1370 cm
1 re-
gions were assigned to the asymmetric and symmetric
stretching modes of carboxylate groups, respectively
[60,61]. The separations between the asymmetric and sym-
metric stretching frequencies, Dm (masym–msym ranges from
246 to 185 cm
1), are indicative of the fact that COO

groups from phthalate groups have bridging O atoms
[62]. Such absorptions have already been reported for other
phthalate complexes with aromatic amines (1620–
1520 cm
1) [21,22]. IR spectrum of complex 1 also showed
a strong and broad m(O–H) stretching band around
3479 cm
1 confirming the presence of the water solute
molecules.
3.3. Catalytic oxidation of cyclohexene
Choosing cyclohexene as a model substrate, oxidation
reactions were carried out in acetone at room temperature
under magnetic stirring in the presence of 1 and 2 as the
catalyst using 30% H2O2. The evolution of the reactions
was monitored by GC analysis of solution samples taken
periodically to determine the concentrations of the various
oxidation products. In a typical experiment, 1 ml of hydro-
gen peroxide (30%) was added to the reaction mixture con-
taining cyclohexene (1 ml) and catalyst (39 mg) in 1 ml
acetone. The results of the investigations are summarized
in Table 3. In the case of 1 the distribution of the products
was strongly dependent on the ratio of [C6H10] to [H2O2].
1220 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222

Fig. 4. Fragment of the layer formed through N–H  O interactions in structure 2. Hydrogen atoms are omitted for clarity and hydrogen bonds are
indicated by dotted lines.

Table 3
Catalytic oxidation of cyclohexene with H2O2a
Catalyst Run Ratio C6H10:H2O2 Products (%)b
Alkene Epoxide Alcohol Ketone
1 1c 1:12 0.76 0.49 5.32 93.4
2c 1:9 6.13 1.49 6.78 85.6
3c 1:4.5 40.5 4.67 11.4 43.4
4d 1:9 0.85 8.39 3.06 87.7
5e 1:9 2.01 11.3 11.5 75.2
2 6e 1:9 38.8 1.94 18.7 40.6
a
Reaction conditions: substrate (1 mmol), catalyst (0.1 mmol), temperature (22 C).
b
Ratio of the different products in the reaction was determined by GC analysis. Products were identified by GC–MS.
c
Acetone – 1 ml, 48 h.
d
Acetone – 0.5 ml, 1 h.
e
Acetone – 1 ml, 1 h.

The largest specificity was obtained using catalyst 1 and a
concentration ratio of 1:12. Under these experimental con-
ditions the allylic hydrogen is more reactive than the C@C
double bond, and the reaction proceeds to give mainly the
2-cyclohexen-1-one as the main product and cyclohexene
epoxide with the lowest yield (entry 1, Table 3). In control
experiments, using cyclohexene under identical experimen-
tal conditions, but excluding metal complex, or in the pres-
ence of Cu(CH3COO)2 Æ H2O, did not give any oxidation
products.
OH
metal atoms linked by 1,6-bridging Pht2
ligands. Preli-
minary catalytic investigations of the complexes for the
oxidation of cyclohexene with H2O2 have been undertaken.
The major oxidation product is 2-cyclohexen-1-one with
appreciable amounts of 2-cyclohexen-1-ol depending on
the reaction conditions. The yield of ketone is higher in
the case of the copper complex. A systematic investigation
on the use of the phthalate linker in the synthesis of 3d-me-
tal coordination polymers and their magnetic and catalytic
properties is currently underway.
O

cat. 5. Supplementary material

+ H2O2 O +
4. Conclusion
Two new copper(II) and cobalt(II) coordination poly-
mers based on o-phthalic acid and imidazole have been
synthesized and characterized by X-ray crystallography.
The compounds have a polymeric chain structure with
+
Crystallographic data for the structural analyses have
been deposited with the Cambridge Crystallographic Data
Centre, CCDC Nos. 271720 (1) and 275123 (2). Copies of
this information may be obtained from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
+44 1233 336033; e-mail: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk). Structure factors for 1 and 2
are available from the authors on request.
 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222
Acknowledgment
S.G.B. is grateful to DAAD for financial support to visit
the Max-Planck-Institut für Kohlenforschung, Mulheim an
der Ruhr, Germany.
References
[1] (a) S.R. Batten, R. Robson, Angew. Chem., Int. Ed. 37 (1998) 1460;
(b) P.J. Hagrman, D. Hargman, J. Zubieta, Angew. Chem., Int. Ed.
38 (1999) 2638;
(c) A.J. Blake, N.R. Champness, P. Hubberstey, W.-S. Li, M.A.
Withersby, M. Schroder, Coord. Chem. Rev. 183 (1999) 117;
(d) R. Robson, J. Chem. Soc., Dalton Trans. (2000) 3735;
(e) M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M.
O
Keeffe, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319;
(f) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629;
(g) B. Moulton, M.J. Zaworotko, Curr. Opin. Solid State Mater. Sci.
6 (2002) 117;
(h) Ch. Janiak, J. Chem. Soc., Dalton Trans. (2003) 2781.
[2] (a) M. Fujita, Y.J. Kwon, S. Washizu, K. Ogura, J. Am. Chem. Soc.
116 (1994) 1151;
(b) J.S. Seo, D. Whang, H. Lee, S.I. Jun, J. Oh, Y.J. Jeon, K. Kim,
Nature 404 (2000) 982;
(c) J.M. Tanski, P.T. Wolczanski, Inorg. Chem. 40 (2001) 2026;
(d) O.R. Evans, H.L. Ngo, W. Lin, J. Am. Chem. Soc. 123 (2001)
10395;
(e) B. Xing, M.-F. Choi, B. Xu, Chem. Eur. J. 8 (2002) 5028;
(f) B. Gomez-Lor, E. Gutierrez-Puebla, M. Iglesias, M.A. Monge, C.
Ruiz-Valero, N. Snejko, Inorg. Chem. 41 (2002) 2429;
(g) B. Kesanli, W. Lin, Coord. Chem. Rev. 246 (2003) 305.
[3] N.V. Gerbeleu, Yu.A. Simonov, G.A. Timko, P.N. Bourosh, J.
Lipkowski, S.G. Baka, D.I. Saburov, M.D. Mazus, Russ. J. Inorg.
Chem. 44 (1999) 1191.
[4] Yu.A. Simonov, M. Gdaniec, I.G. Filippova, S.G. Baca, G.A.
Timco, N.V. Gerbeleu, Russ. J. Coord. Chem. 27 (2001) 353.
[5] S.G. Baca, Yu.A. Simonov, N.V. Gerbeleu, M. Gdaniec, P.N.
Bourosh, G.A. Timco, Polyhedron 20 (2001) 831.
[6] S.G. Baca, I.G. Filippova, N.V. Gerbeleu, Yu.A. Simonov, M.
Gdaniec, G.A. Timco, O.A. Gherco, Yu.L. Malaestean, Inorg. Chim.
Acta 344 (2003) 109.
[7] S.G. Baca, I.G. Filippova, O.A. Gherco, M. Gdaniec, Yu.A.
Simonov, N.V. Gerbeleu, P. Franz, R. Basler, S. Decurtins, Inorg.
Chim. Acta 357 (2004) 3419.
[8] S.G. Baca, S.T. Malinovskii, P. Franz, Ch. Ambrus, H. Stoeckli-Evans,
N.V. Gerbeleu, S. Decurtins, J. Solid State Chem. 177 (2004) 2841.
[9] Yu.A. Simonov, S.G. Baca, I.G. Filippova, M. Gdaniec, O.A.
Gherco, N.V. Gerbeleu, Russ. J. Coord. Chem. 30 (2004) 727.
[10] S.G. Baca, I.G. Filippova, Ch. Ambrus, M. Gdaniec, Yu.A. Simonov,
N. Gerbeleu, O.A. Gherco, S. Decurtins, Eur. J. Inorg. Chem. (2005)
3118.
[11] M.B. Cingi, C. Guastini, A. Musati, N. Nardelli, Acta Crystallogr. B
26 (1970) 1836.
[12] C.K. Prout, J.R. Carruthers, F.J.C. Rossotti, J. Chem. Soc. (1971)
3350.
[13] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini, Acta
Crystallogr. B 33 (1977) 659.
[14] (a) M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini,
Acta Crystallogr. B 34 (1978) 134;
(b) M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini,
Acta Crystallogr. B 34 (1978) 406.
[15] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini, Acta
Crystallogr. B 34 (1978) 412.
[16] J.W. Bats, A. Kallel, H. Fuess, Acta Crystallogr. B 34 (1978) 1705.
[17] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini, Acta
Crystallogr. B 35 (1979) 312.
1221
[18] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini, Acta
Crystallogr. B 37 (1981) 2159.
[19] I. Krstanovic, L. Karanovic, D. Stojakovic, L. Golic, Cryst. Struct.
Commun. 11 (1982) 1747.
[20] I. Krstanovic, Lj. Karanovic, Dj. Stojakovic, Acta Crystallogr. C 41
(1985) 43.
[21] K. Shakhatreh, E.G. Bakalbassis, I. Brudgam, H. Hartl, J. Mrozinski,
C.A. Tsipis, Inorg. Chem. 30 (1991) 2801.
[22] D. Poleti, Lj. Karanovic, B.V. Prelesnik, Acta Crystallogr. C 49
(1993) 1249.
[23] E.G. Bakalbassis, A. Terzis, Inorg. Chim. Acta 218 (1994) 167.
[24] D.J. Williams, S.J. Maginn, R.J. Davey, Polyhedron 13 (1994) 1683.
[25] G. Smith, A.N. Reddy, K.A. Byriel, C.H.L. Kennard, J. Chem. Soc.,
Dalton Trans. (1995) 3565.
[26] J.L.L. Vaz, G. Duc, M. Petit-Ramel, R. Faure, O. Vittori, Can. J.
Chem. 74 (1996) 359.
[27] D.R. Whitcomb, R.D. Rogers, Inorg. Chim. Acta 256 (1997) 263.
[28] A. Escuer, R. Vicente, F.A. Mautner, M.A.S. Goher, Inorg. Chem.
36 (1997) 1233.
[29] E.G. Bakalbassis, D.G. Paschalidis, C.P. Raptopoulou, V. Tangoulis,
Inorg. Chem. 37 (1998) 4735.
[30] Z.-N. Chen, H.-X. Zhang, K.-B. Yu, B.-S. Kang, H. Cai, C.-Y. Su,
T.-W. Wang, Z.-L. Lu, Inorg. Chem. 37 (1998) 4775.
[31] M.R. Bermejo, M. Fondo, A. Garcı́a-Deibe, A.M. González, A.
Sousa, J. Sanmartı́n, C.A. McAuliffe, R.G. Pritchard, M. Watkinson,
V. Lukov, Inorg. Chim. Acta 293 (1999) 210.
[32] P. Lightfoot, A. Snedden, J. Chem. Soc., Dalton Trans. (1999) 3549.
[33] A.D. Burrows, R.W. Harrington, M.F. Mahon, C.E. Price, J. Chem.
Soc., Dalton Trans. (2000) 3845.
[34] M. Devereux, M. McCann, V. Leon, M. Geraghty, V. McKee, J.
Wikaira, Met. Based Drugs 7 (2000) 275.
[35] Y. Zhang, J. Li, Q. Su, Q. Wang, X. Wu, J. Mol. Struct. 516 (2000)
231.
[36] E. Suresh, K. Boopalan, R.V. Jasra, M.M. Bhadbhade, Inorg. Chem.
40 (2001) 4078.
[37] H.-X. Zhang, B.-S. Kang, A.-W. Xu, Z.-N. Chen, Z.-Y. Zhou,
A.S.C. Chan, K.-B. Yu, C. Ren, J. Chem. Soc., Dalton Trans. (2001)
2559.
[38] Y. Wan, L. Jin, K. Wang, L. Zhang, X. Zheng, S. Lu, New J. Chem.
(2002) 1590.
[39] J. Yao, W. Huang, B. Li, S. Gou, Y. Xu, Inorg. Chem. Commun. 5
(2002) 711.
[40] S. Wang, Y. Hou, E. Wang, Y. Li, L. Xu, J. Peng, S. Liu, C. Hu,
New J. Chem. 27 (2003) 1144.
[41] C. Ma, C. Chen, Q. Liu, D. Liao, L. Li, L. Sun, New J. Chem. 27
(2003) 890.
[42] Y.-H. Wan, L.-P. Jin, K.-Z. Wang, J. Mol. Struct. 649 (2003) 85.
[43] L.-N. Zhu, M. Liang, Q.-L. Wang, W.-Z. Wang, D.-Z. Liao, Z.-H.
Jiang, S.-P. Yan, P. Cheng, J. Mol. Struct. 657 (2003) 157.
[44] Y. Wan, L. Zhang, L. Jin, S. Gao, S. Lu, Inorg. Chem. 42 (2003) 4985.
[45] S.B. Raj, P.T. Muthianh, G. Bocelli, A. Canton, Inorg. Chem.
Commun. 6 (2003) 748.
[46] X. Liu, C. Xie, X. Wang, G. Shen, D. Shen, Inorg. Chem. Commun.
6 (2003) 1433.
[47] A. Thirumurugan, S. Natarajan, J. Chem. Soc., Dalton Trans. (2004)
2923.
[48] H.-L. Liu, H.-Y. Mao, H.-Y. Zhang, Ch. Xu, Q.-A. Wu, G. Li, Y.
Zhu, H.-W. Hou, Polyhedron 23 (2004) 943.
[49] B. Corain, A. Tessari, M. Zecca, J. Mol. Cat. A Chem. 96 (1995) L9.
[50] (a) W.H. Richardson, J. Am. Chem. Soc. 87 (1965) 247;
(b) W.H. Richardson, J. Am. Chem. Soc. 87 (1965) 1096;
(c) R. Hiatt, K.C. Irwin, C.W. Gould, J. Org. Chem. 33 (1968)
1430;
(d) N.A. Jonson, E.S. Gould, J. Am. Chem. Soc. 95 (1973)
5198;
(e) E.J.Y. Scott, J. Phys. Chem. 74 (1970) 1174;
(f) G. Vasvari, D. Gal, J. Chem. Soc., Faraday I 73 (1977)
399.
1222 S.G. Baca et al. / Polyhedron 25 (2006) 1215–1222
[51] B. Corain, E. Scanagatto, M. Basato, G. Valle, A.C. Veronese, S.
Sitran, Inorg. Chim. Acta 148 (1988) 105.
[52] G. Das, R. Shukla, S. Mandal, R. Singh, P.K. Bharadwaj, Inorg.
Chem. 36 (1997) 323.
[53] T. Ohta, T. Tachiyama, K. Yoshizawa, T. Yamable, T. Uchida, T.
Kitagawa, Inorg. Chem. 39 (2000) 4358.
[54] T. Ohta, T. Tachiyama, K. Yoshizawa, T. Yamable, T. Uchida, T.
Kitagawa, Tetrahedron Lett. 41 (2000) 2581.
[55] X. Meng, K. Lin, J. Sun, M. Yang, D. Jiang, F.-S. Xiao, Catal. Lett.
71 (3–4) (2001) 241.
[56] G.M. Sheldrick, SHELXS-97, Program for the Solution of Crystal
Structures, University of Goettingen, Germany, 1997.
[57] G.M. Sheldrick, SHELXL-97, Program for the Refinement of Crystal
Structures, University of Goettingen, Germany, 1997.
[58] W.D. Horrocks, J.N. Ishley, R. Whittle, Inorg. Chem. 21 (1982)
3270.
[59] X.H. Chen, B.-H. Ye, X.-Ch. Huang, Z.-T. Xu, J. Chem. Soc.,
Dalton Trans. (1996) 3465.
[60] K. Nakamoto, Infrared and Raman Spectra of Inorganic
and Coordination Compounds, Wiley, New York, 1986,
p. 236.
[61] R.C. Mehrotra, R. Bohra, Metal Carboxylates, Academic Press, New
York, 1983, p. 48.
[62] G.B. Deacon, R.J. Phillips, Coord. Chem. Rev. 33 (1980) 227.