A 3D supramolecular network of cobalt(II)(bis(4-pyridyl)ethylene) with terephthalate dianions

Article abstract of DOI:10.1016/j.ica.2007.07.037

A three dimensional supramolecular network, {[Co(bpee)(H₂O)₄] · (tp) · 2(H₂O)}_n (1) [bpee = trans-1,2 bis(4-pyridyl)ethylene; tp = terephthalate dianion] has been synthesized and characterized by X-ray single crystal structure, magnetic measurement and thermal analysis. The structure determination reveals that the cobalt(II) ions, bridged by bpee and coordinated by four water molecules, give rise to covalently linked 1D polymeric chain. The parallel chains get involved in H-bonding with tp resulting in a 3D architecture. Upon heating 1, which is pink in color, transforms to [Co(bpee)(tp)] (1a, blue). The deaquated species (1a) reverts on keeping in humid atmosphere. Low temperature magnetic data indicate weak antiferromagnetic coupling.

Full text of DOI:10.1016/j.ica.2007.07.037

Available online at www.sciencedirect.com
Inorganica Chimica Acta 361 (2008) 411–416
www.elsevier.com/locate/ica
Note
A 3D supramolecular network of cobalt(II)(bis(4-pyridyl)ethylene)
with terephthalate dianions
a
b
c
d,
*
Subal Chandra Manna , Ennio Zangrando , Joan Ribas , Nirmalendu Ray Chaudhuri
a
Department of Chemistry, Suri Vidyasagar College, Suri- 731101, Birbhum, West Bengal, India
b
Dipartimento di Scienze Chimiche, University of Trieste, 34127 Trieste, Italy
c
`
Departament de Qu´ımica Inorganica, Universitat de Barcelona, Diagonal, 647, 08028 Barcelona, Spain
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata- 700032, India
d
Received 12 February 2007; received in revised form 23 July 2007; accepted 25 July 2007
Available online 15 August 2007
Abstract
A three dimensional supramolecular network, {[Co(bpee)(H2O)4] Æ (tp) Æ 2(H2O)}n (1) [bpee = trans-1,2-bis(4-pyridyl)ethylene;
tp = terephthalate dianion] has been synthesized and characterized by X-ray single crystal structure, magnetic measurement and thermal
analysis. The structure determination reveals that the cobalt(II) ions, bridged by bpee and coordinated by four water molecules, give rise
to covalently linked 1D polymeric chain. The parallel chains get involved in H-bonding with tp resulting in a 3D architecture. Upon
heating 1, which is pink in color, transforms to [Co(bpee)(tp)] (1a, blue). The deaquated species (1a) reverts on keeping in humid atmo-
sphere. Low temperature magnetic data indicate weak antiferromagnetic coupling.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Cobalt(II); Terephthalate; Crystal structure; Magnetic measurement; Supramolecule
1. Introduction
Among the carboxylates, terephthalate dianion (tp) is
being recently used as efficient ‘‘spacer’’ for its versatile
coordination modes and ability to form large and tightly
bound architecture with specific and directional hydrogen
bond as well as p–p stacking [7]. The combined use of tp
with dipyridyl spacers led to novel architectures, namely,
[Co(4,40-bipy)(tp)]n [8], [Co(bpe)(tp)]n [9], and [Co(bpp)-
(tp)(H2O)2]n [7a] (bpp = 1,3-bis(4-pyridyl)propane). Very
recently, we have reported an inclined interpenetrated 3D
network, {[Co(bpe)(tp)(H2O)2] Æ 2.5(H2O)}n (bpe = 1,2-
bis(4-pyridyl)ethane) [10] showing crystals of low life span.
But inclusion of glycol has resulted in [Co(bpe)(tp)-
(H2O)2] Æ (glycol) [10], having higher thermal stability and
longer shelf life of crystals since glycol functions as selective
H-bonded connector between the opposite walls of the
pore inducing contraction of cavity size and higher symme-
try of the architecture. We have also reported a 3D supra-
molecular network, {[Co(dpyo)(tp)(H2O)2] Æ [Co(H2O)6] Æ
(tp) Æ (H2O)}n [11] (dpyo, 4,40-dipyridyl N,N0-dioxide ) with
unique H-bonded assembly and rare bridging mode of
Higher dimensional metal-organic hybrid materials of
transition metal ions are of great interest owing to their
interesting topologies and potential applications in mate-
rial science [1]. Commonly used synthetic approaches for
such materials are: (a) use of anionic bridging ligands,
which can partially/fully counterbalance the charge of the
metal centers [2]; (b) combination of anionic as well as neu-
tral spacers, which may enhance the dimensionality of
molecular materials [3]; (c) use of only neutral spacers
where charges are counterbalanced by non-coordinating
anions [4]. Research in this field has been carried out by
a number of groups [5] including ours, [6] by using various
carboxylates as anionic bridging ligand.
*
Corresponding author. Fax: +91 33 2473 2805.
E-mail addresses: subalmanna@yahoo.com (S.C. Manna), ezangrando
@units.it (E. Zangrando), joan.ribas@qi.ub.es (J. Ribas), icnrc@iacs.res.
in (N. Ray Chaudhuri).
0020-1693/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2007.07.037

412
S.C. Manna et al. / Inorganica Chimica Acta 361 (2008) 411–416
Table 1
dpyo. The foregoing facts have led us to pursue further on
the chemistry of cobalt(II)-terephthalate using a relatively
longer and rigid dipyridyl spacer such as trans-1,2-bis-
(4-pyridyl)ethylene (bpee). In the present contribution, we
report on the synthesis, crystal structure, magnetic behav-
ior and thermal analysis of a 3D supramolecular network
{[Co(bpee)(H2O)4] Æ (tp) Æ 2(H2O)}n (1).
Crystallographic data and details of structure refinement for complex 1
1
Empirical formula
Formula weight
Crystal system
Space group
C20H26CoN2O10
513.36
triclinic
ꢀ
P1
˚
a (A)
6.752(3)
6.438(2)
13.604(3)
110.65(2)
91.69(2)
96.39(2)
548.4(3)
1
1.554
6.674
186
64.56
˚
b (A)
˚
2. Experimental
c (A)
a (°)
b (°)
c (°)
2.1. Materials
3
˚
V (A )
High purity (98%) trans-1,2-bis(4-pyridyl)ethylene
(bpee) was purchased from Aldrich Chemical Company
Inc. and used without further purification. All other chem-
icals were of AR grade.
Z
Dcalcd (g cmꢀ3
)
l Cu Ka (mmꢀ1
F(000)
)
hmax (°)
Reflections collected
Unique reflections
Rint
5335
1626
0.0760
1603
175
2.2. Physical measurements
Observed [I > 2r(I)]
Parameters
Elemental analyses (carbon, hydrogen and nitrogen)
were performed using a Perkin–Elmer 240C elemental ana-
lyzer. IR spectra were measured using KBr pellets on a
Nicolet 520 FTIR spectrometer. Magnetic measurements
were carried out on polycrystalline samples in a Quantum
Design MPMS XL-5 SQUID magnetometer operating at
a magnetic field of 0.1 T between 2 and 300 K. The diamag-
netic corrections were evaluated from Pascal’s constants.
Thermal analysis was done on a Perkin–Elmer Pyris Dia-
mond system.
Goodness of fit (F2)
R1 [I > 2r(I)]a
wR2
1.067
0.0583
0.1568
0.537, ꢀ0.375
a
3
˚
Residuals (e/A )
a
2
R1(Fo) = RiFoj ꢀ jFci/RjFoj, wR2(Fo2) = [Rw(Fo ꢀ Fc2)2/Rw(Fo2)2]1/2
.
yses [14] and refined by the full-matrix least-squares
method based on F2 with all observed reflections [14]. Most
of the water hydrogens detected on the DFourier map were
restrained with a fixed O–H bond distance (0.85 A). All the
calculations were performed using the WinGX System, Ver
1.70.00 [15].
˚
2.3. Synthesis of complex {[Co(bpee)(H2 O)4] Æ (tp) Æ
2(H2 O)}n (1)
An aqueous solution (5 mL) of disodium terephthalate
(1 mmol, 0.210 g) was added drop wise to an aqueous solu-
tion (5 mL) of Co(NO3)2 Æ 6H2O (1 mmol, 0.291 g) under
stirring condition. To this mixture a methanolic solution
(10 mL) of bpee (1 mmol, 0.182 g) was added and stirred
for 1 h. It was filtered and the filtrate was kept in a CaCl2
desiccator. Orange single crystals suitable for X-ray struc-
ture determination were obtained after a week. They were
separated, washed with ethanol and dried. Yield: 70%.
Anal. Calc. for C20H26CoN2O10 (513.36): C, 46.75; H,
5.06; N, 5.45. Found: C, 46.10; H, 4.96; N, 5.30%. The
infrared spectra exhibited the following absorption bands:
3500–2980 (sbr), 1618 (s), 1556 (vs), 1431(w), 1378(vs),
3. Results and discussion
3.1. Structure description of
{[Co(bpee)(H2O)4] Æ (tp) Æ 2(H2O)}n (1)
The structure determination of the complex 1 reveals
Co(H2O)4 units bridged by bpee ligands with the occur-
rence of 1D coordination polymeric chains running along
the crystallographic c direction. An ORTEP drawing with
atom numbering scheme of the metal coordination sphere,
the dicarboxylate counteranion and the lattice water mole-
cules O3w, is shown in Fig. 1, while a selection of bond
lengths and angles is reported in Table 2. The cobalt(II)
ion, the bpee ligand, and the terephthalate dianion are
located on an inversion center. Besides the two bpee N
donors in trans position, each cobalt(II) in the chain is
coordinated by four water molecules resulting in a CoN2O4
chromophore. The octahedral coordination geometry has
bond angles that do not deviate more than 2° from the
ideal values. The four water molecules, O1w, O2w and
the symmetry related ones, form the equatorial plane
around each metal with Co–O1w and Co–O2w distances
1259(vw), 957(w), 827(w), 758(s), 557(s), 507(w) cmꢀ1
.
2.4. Crystallographic data collection and refinement
Crystal data and details of data collections and refine-
ments for the structure reported are summarized in Table
1. Diffraction data for complex 1 were collected on a Non-
ius DIP-1030H system using Mo Ka radiation. Cell refine-
ment, indexing and scaling of the data sets were carried out
using Denzo [12] and Mosflm [13] programs. The structure
was solved by direct methods and subsequent Fourier anal-
˚
of 2.101(3) and 2.116(3) A, respectively, and the Co–N1

S.C. Manna et al. / Inorganica Chimica Acta 361 (2008) 411–416
413
˚
inter-chain metal–metal distance is 6.438 A. In the tere-
phthalate dianion the carboxylate groups form a dihedral
angle of 11.3(3)° with the phenyl ring. The dicarboxylates
are located among the coordination polymers giving rise
to a 3D structure through an ordered H-bonded scheme
with the water molecules (Fig. 2). It is worthy to note that
the lattice water O3w is involved in a quadruple hydrogen
bonded module, that is, double donor (towards O3 and O4)
and acceptor (from O1w and O2w) H-bonding (Fig. 2,
Table 3). The structure has the same stoichiometry, but a
different crystal packing, of the complexes [{M(4,40- bipy)-
(H2O)4}(C5O5) (H2O)2]n (M = Mn, Fe, Co) [16]. In the
latter derivatives the croconate dianions, engaged in a
H-bonding scheme, are sandwiched between bipy rings of
˚
adjacent chains (distance of about 3.4 A) and take part in
p–p interactions. On the other hand, in the present complex
no such interaction is detected (Figs. 2 and 3). The
(shorter) distance between the centroids of bpee rings and
Fig. 1. ORTEP diagram (40% thermal ellipsoid) with atom labeling
scheme of complex 1, the metal is located on an inversion center
[symmetry code (0) ꢀx,2 ꢀy,ꢀz].
˚
terephthalate dianion is 4.802(3) A and the dihedral angle
formed by their mean planes is 34.57°. Thus, the crystal
packing is driven only by the H-bonding scheme involving
the water molecules.
Table 2
˚
Selected bond distances (A) and angles (°) in complex 1
Co–O(1w)
Co–O(2w)
Co–N(1)
2.101(3)
2.116(3)
2.119(3)
O(1w)–Co–O(2w)
O(1w)–Co–O(2w0)
O(1w)–Co–N(1)
O(1w)–Co–N(10)
O(2w)–Co–N(1)
O(2w)–Co–N(10)
89.81(11)
90.19(11)
89.23(11)
90.77(11)
92.35(11)
87.65(11)
3.2. Magnetic properties
O(1w0)–Co–O(1w)
O(2w)–Co–O(2w0)
N(1)–Co–N(10)
180.0
180.0
180.0
The vMT versus T plot for 1 (vM is the molar magnetic
susceptibility for one CoII ion) is shown in Fig. 4. vMT
value, which is 3.62 cm3 molꢀ1 K at 300 K, continuously
decreases and becomes 2.1 cm3 molꢀ1 K at 2 K.
Symmetry code (0) ꢀx,2 ꢀ y,ꢀz.
Based on the reasoning already reported by us [7a] with
regard to the calculation of an estimated J value, we have
used the two-exponential Rueff expression [17,18],
vMT = Aexp(ꢀE1/kT) + Bexp(ꢀE2/kT) [where A + B
equals the Curie constant (ꢁ2.8–3.4 cm3 molꢀ1 K for octa-
hedral cobalt(II) ions), and E1, E2 represent the ‘‘activation
energies’’ corresponding to the spin orbit coupling and the
antiferromagnetic exchange interaction], which is suitable
for any temperature greater than the possible Tc [17,18].
The best fit values obtained with this procedure are:
A + B = 3.52 cm3 molꢀ1 K, in good agreement with those
given in the literature for the Curie constant (C ꢁ 2.8–
.4 cm3 molꢀ1 K) [17,18]; E1/k = 40.1 K, that is, of the same
magnitude to those reported by Rueff et al. for several
one- and two-dimensional cobalt(II) complexes [18]. As
the value found for the antiferromagnetic exchange interac-
tion is very weak (E2/k = 0.28 K), corresponding to J =
ꢀ0.56 K (=ꢀ0.81 cmꢀ1), according to the Ising chain
Fig. 2. Perspective view of crystal packing of 1 [dotted lines indicate
H-bonds].
˚
distance (2.119(3) A) shows a comparable value. The bpee
presents coplanar atoms and separates the cobalt atoms
˚
along the chain by 13.604(3) A (axis c), while the shortest
Table 3
˚
H-bond distances (A) and angles (°) in complex 1
D–H
d(D–H)
d(H. . .A)
\DHA
d(D. . ..A)
A
Symmetry code
O1w–H11
O1w–H12
O2w–H21
O2w–H22
O3w–H31
O3w–H32
0.89
0.89
0.88
0.87
0.89
0.89
1.813
1.923
1.898
1.922
1.954
1.893
170.12
170.76
171.77
173.59
164.39
169.48
2.693
2.807
2.771
2.785
2.820
2.774
O3
O3w
O4
O3w
O4
O3
[ꢀx + 1,ꢀy + 1,ꢀz]
[x,y + 1,z]
[ꢀx + 1,ꢀy + 2,ꢀz]
[x,y + 1,z]

414
S.C. Manna et al. / Inorganica Chimica Acta 361 (2008) 411–416
5 T (Fig. 4, inset), which is in perfect agreement with the
values reported [17].
3.3. Thermal study
Complex 1 (pink) upon heating loses two lattice water
and four coordinated water molecules in one step (70–
120 °C) yielding a blue species, 1a (solid state electronic
spectra: 19250, 17960, 13990–15460, and 8825 cmꢀ1; leff,
4.80 BM at 300 K), which is stable up to 200 °C. Species
1a reverts on exposure to humid (RH ꢂ80%) atmosphere.
The sharp deaquation does not allow to generate {[Co(bpee)-
(H2O)4](tp)}n as intermediate species in the solid state.
Crystal structure is in favor of such type of deaquation
as coordinated as well as lattice water molecules are invol-
ved in H-bonding with encapsulated tp. The IR spectra of 1
and 1a show a slight shift in m(COO) band supporting
de-encapsulation of tp after release of water molecules to
maintain the tetrahedral geometry of cobalt(II).
Fig. 3. View of crystal packing down a-axis showing the H-bonding
scheme between terephthalate dianion and water molecules (of the –
Co(H2O)4–bpee– polymers only water molecules shown; larger sphere
represents the lattice water molecule O3w).
3.6
3.2
2.5
4. Conclusion
2.0
In this investigation we report another contribution to
the study of cobalt(II)-terephthalate coordination poly-
mers using N,N0-donor ligands. The structure determina-
tion reveals that tp does not get involved in coordination
and remains as lattice moiety in between the
–[Co(H2O)4bpee]n– chains. But extensive hydrogen bond-
ing among the coordinated/lattice water molecules and lat-
tice tp enhances the dimensionality to 3D. A comparison of
available Co(II)-terephthalate structures (Table 4) reveals
that the topology and the dimensionality of the network
not only depend on the associated coligands but also on
the number of coordinated water molecules. It is apparent
that the augmentation of coordinated water molecules
induces a decrease in dimensionality from 3D to 2D and
ultimately to 1D. Moreover, the long ligands, i.e., rigid
4,40-bipy/flexible bpp/bpe favor the interpenetration.
Although it is difficult to rationalize these results, the rela-
tively longer rigid bpee used in the present system seems to
2.8
1.5
β
T
M/N
1.0
0.5
0.0
M
χ
2.4
2.0
0
10000 20000 30000 40000 50000
/ G
H
0
50
100
150
200
250
300
T
/ K
Fig. 4. vMT versus T plot for complex 1. The solid line represents the best-
fit. Inset: Plot of the reduced magnetization (M/Nb) versus H at 2 K for
complex 1.
approximation, vMT µ exp(J/2kT). The small J value is
compatible with the long bridging ligand. The reduced
magnetization curve, M/Nb, at 2 K tends to 2.5 Nb at
Table 4
Cobalt-terephthalate networks in combination with dipyridyl spacers
Complex
Description
Reference
[Co(4,40-bipy)(tp)]n
[Co(bpe)(tp)]n (bpe = 1,2-bis(4-
pyridyl)ethane)
Two fold interpenetrated 3D coordination polymer formed by tp and 4,40-bipy
Two fold interpenetrated 3D net of cuboidal building blocks formed by tp and bpe
[8]
[9]
{[Co(bpe)(tp)(H2O)2] Æ 2.5(H2O)}n
Inclined interpenetrated 2D sheets of tp and bpe having (4,4) topology. Water molecules [10]
fill the channels in the interlocked 3D structure
{[Co(bpe)(tp)(H2O)2] Æ (glycol)}n
Inclined interpenetrated 2D sheets of tp and bpe having (4,4) topology. Glycol molecules [10]
fill the channels in the interlocked 3D structure
[Co(bpp)(tp)(H2O)2]n (bpp = 1,3-bis(4-
pyridyl)propane)
Parallel interpenetrated 2D layers of tp and bpp having (4,4) topology leading to a 3D
supramolecular network through H-bonding interactions
[7a]
{[Co(dpyo)(tp)(H2O)2] Æ [Co(H2O)6]
Æ (tp) Æ (H2O)}n
1D coordination polymer (built up by Co(II) ions doubly bridged tp and dpyo oxygen). A [11]
3D supramolecular network originated through H-bonds with [Co(H2O)6]2+, lattice tp
and water molecules
{[Co(bpee)(H2O)4] Æ (tp) Æ 2(H2O)}n
(bpee = trans-1,2-bis(4-pyridyl)ethylene)
1D polymeric chain –[Co(H2O)4–bpee]–. A 3D supramolecular network is achieved by
H-bond interactions of lattice tp and water molecules
this work

S.C. Manna et al. / Inorganica Chimica Acta 361 (2008) 411–416
415
(f) S.-Y. Yu, H. Huang, H.-B. Liu, Z.-N. Chen, R. Zhang, M. Fujita,
Angew. Chem., Int. Ed. 42 (2003) 686;
(g) M. Tominaga, K. Suzuki, M. Kawano, T. Kusukawa, T. Ozeki, S.
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impede tp to enter in the coordination network and fix it
through encapsulation.
Acknowledgements
(h) J.J. Perry, G.J. McManus, M.J. Zaworotko, Chem. Commun.
(2004) 2534;
(i) J. Lu, A. Mondal, B. Moulton, M.J. Zaworotko, Angew. Chem.,
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The authors are thankful to Council of Scientific and
Industrial Research, New Delhi, and Spanish Government
(Grant CTQ2006/03949BQU) for financial support.
[6] (a) S. Sain, T.K. Maji, G. Mostafa, T.-H. Lu, N. Ray Chaudhuri,
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Chim. Acta 357 (2004) 1593;
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Appendix A. Supplementary data
CCDC 634486 contains the supplementary crystallo-
graphic data. The data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary
data associated with this article can be found, in the online
version, at doi:10.1016/j.ica.2007.07.037.
(h) S. Konar, E. Zangrando, N. Ray Chaudhuri, Inorg. Chim. Acta
355 (2003) 264.
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