Synthesis and structures of CoII, NiII, and CuII coordination frameworks formed by a flexible 1,3-phenylenediacetic acid ligand

Article abstract of DOI:10.1016/j.molstruc.2010.02.019

Three new compounds of Co^II, Ni^II and Cu^II with a flexible dicarboxylate building block 1,3-phenylenediacetate, along with 4,4′-bipyridine, or 4,4′-trimethylenedipyridine co-ligands, with the formula {[Co₂(4,4′-bipy)₂(1,3-pda)₂]·1.5H₂O}_n (1), {Ni(4,4′-bipy)(1,3-pdaH)₂(CH₃CH₂OH)₂}_n (2), and {Cu(tmdp)(1,3-pda)}_n (3), (where, 1,3-pda = 1,3-phenylenediacetate, 4,4′-bipy = 4,4′-bipyridine, and tmdp = 4,4′-trimethylenedipyridine) have been synthesized and structurally characterized. Compound 1 was synthesized hydrothermally at 180 °C, whereas 2 and 3 were synthesized at room temperature in H₂O/ethanol medium. The 2D coordination network of 1 is formed by pillaring the 1D staircase Co₂(1,3-pda)₂ chain by 4,4′-bipy, whereas the 3D supramolecular framework 2 is constituted by connecting the 2D H-bonded Ni(1,3-pdaH)₂(C₂H₅OH)₂ sheets. Compound 3 shows an unusual 2D network which is built by the flexible 1,3-pda and tmdp linkers by connecting Cu₂(1,3-pda)₂ dimeric building unit.

Full text of DOI:10.1016/j.molstruc.2010.02.019

Journal of Molecular Structure 976 (2010) 168–173
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis and structures of CoII, NiII, and CuII coordination frameworks formed
by a flexible 1,3-phenylenediacetic acid ligand
*
*
C.M. Nagaraja, T.K. Maji , C.N.R. Rao
Chemistry and Physics of Materials Unit, and New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064, India
a r t i c l e i n f o
a b s t r a c t
Three new compounds of CoII, NiII and CuII with a flexible dicarboxylate building block 1,3-phenylenedi-
acetate, along with 4,40-bipyridine, or 4,40-trimethylenedipyridine co-ligands, with the formula {[Co2(4,40-
bipy)2(1,3-pda)2]ꢀ1.5H2O}n (1), {Ni(4,40-bipy)(1,3-pdaH)2(CH3CH2OH)2}n (2), and {Cu(tmdp)(1,3-pda)}n
(3), (where, 1,3-pda = 1,3-phenylenediacetate, 4,40-bipy = 4,40-bipyridine, and tmdp = 4,40-trimethylen-
edipyridine) have been synthesized and structurally characterized. Compound 1 was synthesized hydro-
thermally at 180 °C, whereas 2 and 3 were synthesized at room temperature in H2O/ethanol medium. The
2D coordination network of 1 is formed by pillaring the 1D staircase Co2(1,3-pda)2 chain by 4,40-bipy,
whereas the 3D supramolecular framework 2 is constituted by connecting the 2D H-bonded Ni(1,3-
pdaH)2(C2H5OH)2 sheets. Compound 3 shows an unusual 2D network which is built by the flexible 1,3-
pda and tmdp linkers by connecting Cu2(1,3-pda)2 dimeric building unit.
Article history:
Received 26 December 2009
Received in revised form 8 February 2010
Accepted 8 February 2010
Available online 13 February 2010
Dedicated to Professor A.J. Barnes
Keywords:
CoII-complex
NiII-complex
CuII-complex
Flexible dicarboxylate
Pyridyl linkers
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
frameworks are solely determined by the connectivity of the
organic linkers. There has been a thrust to generate functional
Metal–organic coordination frameworks constitute an impor-
tant class of materials which have attracted considerable attention
in the last two decades because of their wide range of applications
in catalysis [1–4], gas sorption [5–7], and size selective separation
[8–12]. These materials show interesting structural flexibility, tun-
able pore size with different polarity depending upon the nature of
the organic struts [13–18]. Materials with flexible frameworks,
showing dynamic behavior, such as framework breathing [19],
guest responsive structural asymmetry [20–23], and single crys-
tal-to-single crystal structural transformation [24–26] may find
potential applications in molecular recognition and separation
studies. One of the keys to structural flexibility is to exploit H-
frameworks by tuning the reaction parameters [35]. Aromatic
dicarboxylates such as 1,2-, 1,3- and 1,4-benzenedicarboxylates
(bdc) ligands have been extensively used for the construction of
metal–organic coordination networks [36–41]. However, the flexi-
ble analogues 1,2-, 1,3- and 1,4-phenylenediacetic acids (pda) are
less explored [35]. The structural diversity of these linkers guided
us to carry out the present study. In this paper, we report the syn-
thesis and structures of {[Co2(4,40-bipy)2(1,3-pda)2]ꢀ1.5H2O}n, (1),
{Ni(4,40-bipy)(1,3-pdaH)2(CH3CH2OH)2}n (2), and {Cu(tmdp)(1,3-
pda)}n (3), coordination frameworks with 1,3-pda and 4,40-bipy,
or tmdp as co-ligands.
bonding,
p–p
interactions as noncovalent interactions, along with
2. Experimental
directional covalent forces [27].
Metal carboxylates are known to form a wide range of metal–
organic hybrid materials [28–30]. A combination of mixed ligands
such as di-, tri-, or tetra-carboxylates along with pyridyl based
linkers allow the design of supramolecular networks with different
network topologies, flexible pore sizes with diverse functionalities
[31–33]. It has been proposed that one can design and synthesize a
number of coordination frameworks by a suitable combination of
organic linkers by varying the reaction stoichiometry, temperature,
solvents, etc. [34]. The material properties of such coordination
2.1. Materials
Co(NO)3ꢀ6H2O, Ni(NO)3ꢀ6H2O, Cu(NO)3ꢀ2.5H2O, 1,3-phenylen-
edicarboxylic acid, 4,40-bipyridine, and 4,40-trimethylenebipyri-
dine were purchased from Aldrich Chemical Co. and used as
received without further purification.
2.2. Physical measurements
Elemental analyses were carried out using a Thermo Scientific
Flash 2000 CHN analyzer. IR spectra of the compounds were
recorded on a Bruker IFS 66v/S spectrophotometer using the KBr
* Corresponding authors. Tel.: +91 80 23653075/2208276; fax: +91 80 22082760.
E-mail addresses: tmaji@jncasr.ac.in (T.K. Maji), cnrrao@jncasr.ac.in (C.N.R. Rao).
0022-2860/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.02.019

C.M. Nagaraja et al. / Journal of Molecular Structure 976 (2010) 168–173
169
pellets in the region 4000–400 cmꢁ1. Thermogravimetric analysis
(TGA) was carried out on Mettler Toledo TGA850 instrument in
the temperature range of 25–650 °C under nitrogen atmosphere
(flow rate of 50 mL/min) at a heating rate of 3 °C/min.
gen atoms were refined anisotropically. In all cases (1–3) hydrogen
atoms were fixed by HFIX and placed in ideal positions. The coor-
dinates, anisotropic displacement parameters, and torsion angles
for all of the compounds are submitted in CIF format. All crystallo-
graphic and structure refinement data of the compounds are sum-
marized in Table 1. All calculations were carried out using SHELXL
97 [45], PLATON [46], SHELXS 97 [47], and WinGX system, Ver
1.70.01 [48].
2.3. Synthesis
2.3.1. Synthesis of {[Co2(4,40-bipy)2(1,3-pda)2]ꢀ1.5H2O}n (1)
Compound 1 was synthesized under hydrothermal conditions
at 180 °C. About 0.194 g (1 mmol) of 1,3-phenylenediacetic acid
was dissolved in 6 mL water by adding 0.080 g (2.0 mmol) of
NaOH. To the solution, 0.099 g (0.5 mmol) of 4,40-bipyridine was
added and stirred for 30 min. To this mixture 0.291 g (1 mmol) of
Co(NO)3ꢀ6H2O was added and stirred for 30 min. Then reaction
mixture was transferred to a 25 mL Teflon bomb, which was sub-
sequently heated at 180 °C. After 3 days, pink block crystalline so-
lid of 1 was isolated. The solid was filtered and washed several
times with water (yield: 60%, based on Co). Anal. calcd for
3. Results and discussion
3.1. Structural description of {[Co2(4,40-bipy)2(1,3-pda)2]ꢀ1.5H2O}n (1)
ꢀ
Compound 1 crystallizes in a triclinic system with the P1 space
group. It has a 2D coordination network bridged by 1,3-pda and
4,40-bipy linkers. There are two crystallographically independent
octahedral CoII centers in the asymmetric unit, which are bridged
by the two different 1,3-pda dicarboxylates, one of which chelates
to two CoII centers and other one connects three CoII centers
through syn–syn bridging and monodentate carboxylate binding
(Fig. 1a and c). The cis and trans conformations of the two different
1,3-pdas form a 1D staircase like chain (Fig. 1b) which is further
pillared by 4,40-bipy linker form a 2D coordination network
(Fig. 1d). Thus, both the CoII centers are chelated to one 1,3-pda
and bridged by two other 1,3-pdas through monodentate carboxyl-
ate binding and two 4,40-bipy linkers forming a slightly distorted
CoO4N2 octahedron. The Co1–O and Co1–N bond distances are in
the range of 2.012(4)–2.225(4) Å and 2.157(5)–2.158(5) Å, respec-
tively. The Co2–O and Co2–N bond distances are in the range of
2.019(5)–2.165(5) Å and 2.139(5)–2.167(5) Å, respectively. The de-
gree of distortion is reflected in cisoid and transoid angles around
CoII centers, which are in the range of 59.11(17)–116.7(2)° and
148.00(16)–178.67(18)°, respectively. The distance between two
adjacent CoII centers along 4,40-bipy is 11.425 Å and along the
1,3-pda bridging is about 8.047 Å. The 2D network contains 1D
dumbbell shape channels along the crystallographic a-axis occu-
pied by the guest water molecules (Fig. 1e). Selected bond lengths
and angles are summarized in Table 2.
C
80H64Co4N8O19; C, 55.29; H, 4.41; N, 6.45. Found: C, 55.21; H,
4.19; N, 6.32%. FT-IR (KBr pellet, 4000–400 cmꢁ1): 3428 (br),
3037 (w), 1603 (s), 1551 (m), 1412 (s), 1214 (w), 2201 (w), 815
(m), 718 (m), 631 (m), 501 (w).
2.3.2. Synthesis of {Ni(4,40-bipy)(1,3-pdaH)2(CH3CH2OH)2}n (2)
1,3-Phenylenediacetic acid (1 mmol, 0.184 g) and 4,40-bipyri-
dine (0.5 mmol, 0.078 g) were mixed in 100 mL ethanol and stirred
for 30 min. Ni(NO3)2ꢀ6H2O (1 mmol, 0.290 g) was dissolved in
100 mL of H2O and 2 mL of this NiII solution was slowly and care-
fully layered with the above mixed ligand solution using 1 mL buf-
fer (1:2 of water and EtOH) solution. Light sky blue crystals were
obtained after 1 month. The crystals were separated washed with
EtOH–water (1:1) mixture and dried in air. Yield (55%). Anal. calcd
for C34H36N2NiO10; C, 59.12; H, 5.25; N, 4.06. Found: C, 58.84; H,
5.10; N, 4.02%. FT-IR (KBr pellet, 4000–400 cmꢁ1): 2969 (s), 1725
(s), 1608 (s), 1551 (s), 1536 (s), 1487 (m), 1392 (m), 1320 (m),
1167 (m), 1047 (m), 817 (m), 708 (m), 635 (m), 502 (w).
2.3.3. Synthesis of {Cu(tmdp)(1,3-pda)}n (3)
Compound 3 was synthesized adopting a procedure similar to
that of 2. The 1,3-phenylenediacetic acid (1 mmol, 0.184 g) and
4,40-trimethylenedipyridine (0.5 mmol, 0.099 g) were mixed and
stirred for 30 min. Cu(NO3)2ꢀ2ꢀ5H2O (1 mmol, 0.232 g) was dis-
solved in 100 mL of H2O and 2 mL of this CuII solution was slowly
and carefully layered with the above mixed ligand solution using
1 mL buffer (1:2 of water and EtOH) solution. Blue block shaped
crystals were obtained after 2 weeks. The crystals were separated
washed with EtOH–water (1:1) mixture and dried in air. Yield
(65%). Anal. calcd for C23H22CuN2O4; C, 60.90; H, 4.82; N, 6.14.
Found: C, 60.22; H, 4.70; N, 5.05. FT-IR (KBr pellet, 4000–
400 cmꢁ1): 3098 (w), 3060 (w), 2960 (s), 1623 (s), 1550 (s), 1480
(m), 1389 (m), 1315 (m), 1188 (m), 812 (m), 718 (m), 615 (m).
Table 1
Crystal and structure refinement data for 1, 2, and 3.
Empirical formula
Mr
C80H70Co4N8O19
1677.11
C34H36NiN2O10
691.34
Monoclinic
P21/n (No. 14)
11.2945(6)
10.0757(6)
14.8167(10)
90
103.926(4)
90
1636.58(17)
2
C23H22CuN2O4
453.98
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
P1 (No. 2)
Orthorhombic
Pbcn (No. 60)
21.8967(5)
10.8448(3)
16.9551(4)
90.00
ꢀ
11.4131(3)
12.2396(3)
14.6560(4)
66.683(1)
83.239(1)
80.226(1)
1849.94(8)
1
a
(°)
b (°)
90.00
90.00
c
(°)
V (Å3)
Z
4026.25(17)
8
2.4. X-ray crystallography
T (K)
293(2)
1.505
0.961
860
28.4
0.71073
35,965
8857
173(2)
1.403
0.653
724
293(2)
1.498
1.118
1880
19.6
0.71073
27,430
Single crystals of 1, 2, and 3 suitable for X-ray diffraction were
carefully selected after examination under an optical microscope
and then mounted on a thin glass fiber with commercially avail-
able super glue. The structural data were collected on a Bruker
Smart-CCD diffractometer equipped with a normal focus, 2.4 kW
Dc (g cmꢁ3
)
l
(mmꢁ1
)
F(000)
hmax (deg)
k (Mo K ) (Å)
Tot. data
25.1
0.71073
15,570
2915
a
sealed tube X-ray source with graphite monochromated Mo K
a
Unique data, Rint
1753
radiation (k = 0.71073 Å) operating at 50 kV and 30 mA. The data
acquisition were done using SMART software and SAINT software
was used for data reduction [42]. The empirical absorption correc-
tions were made using the SADABS program [43]. All the structures
were solved by SIR-92 and refined by a full matrix least-squares
method using SHELXL [44]. For all the compounds, the non-hydro-
Data [I > 2
r
(I)]
6283
2218
1572
0.0230
0.0571
1.05
Ra
0.0780
0.2618
1.10
0.0368
0.0893
1.03
b
Rw
S
a
R =
Rw = [
R
(|Fo|ꢁ|Fc|)/
R|Fo|.
b
R
w(|Fo| ꢁ |Fc|)2/
R .
w|Fo|2]1/2

170
C.M. Nagaraja et al. / Journal of Molecular Structure 976 (2010) 168–173
Fig. 1. Structure of {[Co2(4,40-bipy)2(1,3-pda)2]ꢀ1.5H2O}n, (1): (a) view of the coordination environment around CoII center, only the nitrogen atoms of 4,40-bipy are shown; (b)
view of the staircase type 1D chain formed by [Co2(1,3-pda)2]; (c) the stacking of ladder like 1D chains [Co2(1,3-pda)2]; (d) view of the 2D network constructed by 1D ladder
[Co2(1,3-pda)2] which is pillared by 4,40-bipy and (e) view of the 2D network with dumbbell shape channels occupied by guest water molecules along the a-axis.
3.2. Structural description of {Ni(4,40-bipy)(1,3-pdaH)2(CH3CH2OH)2}n
(2)
(O5 and O5a; a = 2 ꢁ x, ꢁ y, 2 ꢁ z) from two ethanol molecules
(Fig. 2a). The 1,3-pdaH and EtOH molecules are in trans to each
other. Here 1,3-pdaH acts as a monodentate nonbridging ligand
and free –COOH group connects to another COO group attached
to another NiII center through O2. . .H4A–O4 H-bonding interac-
tions forming a 2D corrugated sheet lying in the crystallographic
bc plane (Fig. 2b). The O2. . .H4A, O2–O4 distances are 1.790 and
2.587(3) Å, respectively. These 2D Ni(1,3-pdaH)2(CH3CH2OH)2
sheets are furthered pillared by the 4,40-bipy resulting in a 3D
supramolecular framework (Fig. 2c). In the 3D framework, NiII cen-
ters are in the special positions, with a distance of 11.294 Å
through 4,40-bipy linker. The Ni1–O1 bond distance of coordinated
Compound 2 crystallizes in a monoclinic system with the P21/n
space group. The asymmetric unit of 2 consists of a NiII ion, two
1,3-pdaH ligands, one bridging 4,40-bipy linker and two ethanol
molecules. Structure determination of 2 reveals a 1D coordination
chain bridged by 4,40-bipy linker. The geometry around each NiII is
a nearly distorted octahedron formed by two nitrogen atoms (N1
and N1a) of two bridging 4,40-bipy ligands in axial positions and
the equatorial positions are occupied by the two oxygen (O1 and
O1a) atoms from two 1,3-pdaH ligands and two oxygen atoms

C.M. Nagaraja et al. / Journal of Molecular Structure 976 (2010) 168–173
171
Table 2
carboxylate group of 1,3-pdaH ligand is 2.0626(16) Å and the Ni1–
O5 bond distance of coordinated ethanol is 2.0965(17) Å. The se-
lected bond lengths and angles are summarized in Table 3.
Bond distances (Å) and angles (ꢁ) for {[Co2(4,40-bipy)2(1,3-pda)2]ꢀ1.5H2O}n (1).
Co1–O1
Co1–N1
Co1–O8#2
Co2–O3
Co2–O5
2.225(4)
2.158(5)
2.012(4)
2.224(5)
2.019(5)
2.139(5)
Co1–O2
2.182(5)
2.157(5)
2.030(5)
2.165(5)
2.167(5)
2.027(6)
Co1–N2#1
Co1–O7#3
Co2–O4
Co2–N3
Co2–O6#3
3.3. Structural description of {Cu(tmdp)(1,3-pda)}n (3)
Co2–N4#1
Compound 3 crystallizes in an orthorhombic system with the
Pbcn space group. The structure involves a 2D coordination net-
work of CuII bridged by 1,3-pda and tmdp linkers. The asymmetric
unit consists of a CuII ion, a 1,3-pda ligand and a tmdp linker
(Fig. 3a). Here two 1,3-pda linkers connect two CuII centers through
O1–Co1–O2
59.11(17)
89.10(19)
90.1(2)
88.94(18)
94.51(19)
116.7(2)
97.50(18)
148.00(16)
178.51(19)
91.7(2)
91.03(17)
114.23(19)
93.36(19)
94.55(19)
153.11(19)
O1–Co1–N1
92.17(19)
86.90(16)
156.6(2)
89.12(18)
92.2(2)
84.01(18)
178.67(18)
87.20(18)
89.4(2)
O4–Co2–N4#1
O4–Co2–O6#3
O5–Co2–N3
O1–Co1–N2#1
O1–Co1–O8#2
O1–Co1–O7#3
O5–Co2–N4#1
O2–Co1–N2#1
N3–Co2–N4_#1
O6#5–Co2–N3
O8#3–Co1–N1
O7#5–Co1–N1
O7#5–Co1–N2#1
O3–Co2–O4
O2–Co1–N1
O5–Co2–O6#3
O2–Co1–O8#2
O2–Co1–O7#3
N1–Co1–N2#1
O6#5–Co2–N4#1
O8#3–Co1–N2#1
O7#5–Co1–O8#2
O3–Co2–O5
l2–O(3) bridges forming a Cu2(1,3-pda)2 secondary building unit,
and each dimer is further connected to four other dimers through
1,3-pda and tmdp linkers forming a wavy-like 2D sheet lying in the
ab plane (Fig. 3b) and the 2D sheets stack along b-axis (Fig. 3c). In
the 2D network, the coordination environment around each CuII is
nearly a distorted octahedron with (4 + 2) geometry. The CuO4N2
chromophore was built by two nitrogen atoms (N1 and N2) of
two bridging tmdp linkers in the axial positions and four oxygen
atoms (O1, O2, O3, and O3a; a = 1/2 + x, 1/2 ꢁ y, ꢁz) from the three
of 1,3-pda in the equatorial positions. The 1,3-pda ligand acts as a
90.0(2)
91.13(19)
59.77(16)
86.05(18)
149.0(2)
O3–Co2–N3
O3–Co2–O6#3
O3–Co2–N4#1
O4–Co2–O5
Symmetry code: 1 = ꢁ1 + x, y, z; 2 = 1 + x, ꢁ1 + y, 1 + z; 3 = ꢁx, 1 ꢁ y, 2 ꢁ z, 5 = ꢁx,
1 ꢁ y, 2 ꢁ z.
tridentate ligand which bridges two CuII centers through
and chelates to another CuII center through (O1, O2) oxygen atoms.
l–O(3)
Fig. 2. Crystal structure of {Ni(4,40-bipy)(1,3-pdaH)2(CH3CH2OH)2}n (2): (a) view of the coordination environment around the NiII center, only the nitrogen atoms of 4,40-bipy
are shown; (b) view of the 2D network formed by the hydrogen bonding interaction of [Ni(1,3-pdaH)(C2H5OH)2] and (c) view of the 3D framework constructed by 2D network
of [Ni(1,3-pdaH)(C2H5OH)2] which is pillared by 4,40-bipy.

172
C.M. Nagaraja et al. / Journal of Molecular Structure 976 (2010) 168–173
Table 3
Table 4
Bond distances (Å) and angles (ꢁ) for {[Ni(4,40-byp)(1,3-pda)2(CH3CH2OH)2]}n (2).
Bond distances (Å) and angles (ꢁ) for {Cu(tmdp)(1,3-pda)}n (3).
Ni1–O1
Ni1–N1
Ni1–O5#1
2.0626(16)
2.0936(19)
2.0965(17)
Ni1–O5
Ni1–O1#1
Ni1–N1#1
2.0965(17)
2.0626(16)
2.0936(19)
Cu1–O1
Cu1–N1
Cu1–N2#1
1.968(2)
2.018(3)
2.021(2)
Cu1–O2
Cu1–O3#1
Cu1–O3#3
2.759(2)
2.001(2)
2.367(2)
O1–Ni1-–O5
92.13(6)
180.00
O1–Ni1–N1
O1–Ni1–O5#1
O5–Ni1–N1
O5–Ni1–O5#1
O1#1–Ni1–N1
N1–Ni1–N1#1
O1#1–Ni1–N1#1
90.32(7)
87.87(6)
94.08(7)
180.00
89.68(7)
180.00
O1–Cu1–O2
52.71(8)
175.68(9)
100.16(8)
130.68(8)
152.51(7)
165.50(11)
90.01(9)
O1–Cu1–N1
O1–Cu1–N2#1
O2–Cu1–N1
O2–Cu1–N2#1
O3#1–Cu1–N1
O3#4–Cu1–N1
O3#4–Cu1–N2#1
89.17(10)
87.41(10)
78.76(10)
87.98(8)
94.18(10)
98.61(10)
95.85(8)
O1–Ni1–O1#1
O1–Ni1–N1#1
O1#1–Ni1-O5
O5–Ni1–N1#1
O5#1–Ni1–N1
O1#1–Ni1–O5#1
O5#1–Ni1–N1#1
O1–Cu1–O3#1
O1–Cu1–O3#3
O2–Cu1–O3#1
O2–Cu1–O3#3
N1–Cu1–N2#1
O3#1–Cu1–N2#1
89.68(7)
87.87(6)
85.92(7)
85.92(7)
92.13(6)
94.08(7)
90.32(7)
Symmetry code: 1 = 1/2 + x,1/2 ꢁ y, ꢁz, ꢁ1/2 + z, 2 = 5/2 ꢁ x, ꢁ1/2 + y, z, 3 = 5/
2 ꢁ x,1/2 + y, z, 4 = 5/2 ꢁ x,1/2 + y, z.
Symmetry code: 1 = 2 ꢁ x, ꢁy, 2 ꢁ z.
The Cu1–O, Cu1–N bond distances are in the range 1.968(2)–
2.759(2) Å, 2.018(3)–2.021(2) Å, respectively. In the 2D sheet the
nated ethanol molecules, and the subsequent step (300–325 °C) is
due to loss of one molecule of coordinated 4,40-bipy ligand.
Cu. . .Cu distance along the l–O3 bridges is 3.435 Å and it increase
to 11.428 Å by tmdp bridges. The selected bond lengths and angles
are summarized in Table 4.
4. Conclusion
In conclusion, we have synthesized and structurally character-
ized three new metal–organic coordination frameworks of CoII, NiII,
and CuII formed by a flexible dicarboxylate building block, 1,3-
phenylenediacetate along with 4,40-bipyridine, or 4,40-trimethy-
lenedipyridine as co-ligands, by utilizing both hydrothermal and
room temperature synthetic strategies. The different binding mode
of flexible 1,3-pda building unit lead to the formation of 2D net-
work in 1 and 3 and 3D supramolecular framework in 2. All the
three compounds exhibit different network topologies.
3.4. Thermogravimetric analysis (TGA)
The TGA of compounds 1 and 2 was performed under a nitrogen
atmosphere. In Compound 1 the first step (100–175 °C) is due to
the loss of two crystalline water molecules. The second step
(180–300 °C) corresponds to loss of a 4,40-bipy linker, and then
subsequently decomposes to unidentified product. In compound
2 the first step (100–160 °C) corresponds to the loss of two coordi-
Fig. 3. Structure of {Cu(tmdp)(1,3-pda)}n (3): (a) view of the coordination environment around the CuII center; (b) view of the 2D wavy-like network lying in the
crystallographic ab plane. (c) Packing of the 2D wavy-like networks along the crystallographic b direction.

C.M. Nagaraja et al. / Journal of Molecular Structure 976 (2010) 168–173
[16] T.K. Maji, S. Kitagawa, Pure Appl. Chem. 79 (2007) 2155.
173
Acknowledgements
[17] G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, Acc. Chem. Res. 38 (2005)
217.
Authors are thankful to Mr. Prakash Kanoo and Mr. R. Shambu
for their help and discussions. C.M.N. thanks the DRDO, India for
the fellowship.
[18] A.K. Bar, R. Chakrabarty, G. Mostafa, P.S. Mukherjee, Angew. Chem. Int. Ed. 47
(2008) 8455.
[19] C. Serre, F. Millange, C. Thouvenot, M. Noguès, G. Marsolier, D. Louër, G. Férey,
J. Am. Chem. Soc. 124 (2002) 13519.
[20] T.K. Maji, G. Mostafa, R. Matsuda, S. Kitagawa, J. Am. Chem. Soc. 127 (2005)
17152.
Appendix A. Supplementary data
[21] K. Barthelet, J. Marrot, D. Riou, G. Férey, Angew. Chem. Int. Ed. 41 (2002) 281.
[22] K. Uemura, S. Kitagawa, K. Fukui, K. Saito, J. Am. Chem. Soc. 126 (2004) 3817.
[23] X. Lin, A.J. Blake, C. Wilson, X.Z. Sun, N.R. Champness, M.W. George, P.
Hubberstey, R. Mokaya, M. Schroder, J. Am. Chem. Soc. 128 (2006) 10745.
[24] S. Takamizawa, E.-i. Nakata, H. Yokoyama, K. Mochizuki, W. Mori, Angew.
Chem. Int. Ed. 42 (2003) 4331.
[25] B. Rather, M.J. Zaworotko, Chem. Commun. (2003) 830.
[26] E.Y. Lee, M.P. Suh, Angew. Chem. Int. Ed. 43 (2004) 2798.
[27] S. Kitagawa, K. Uemura, Chem. Soc. Rev. 34 (2005) 109.
[28] D. Maspoch, D. Ruiz-Molina, J. Veciana, Chem. Soc. Rev. 36 (2007) 770.
[29] R. Vaidhayanathan, S. Natarajan, C.N.R. Rao, Dalton Trans. (2003) 1459.
[30] A. Thirumurugan, C.N.R. Rao, J. Mater. Chem. 15 (2005) 3852.
[31] K.L. Mulfort, J.T. Hupp, Inorg. Chem. 47 (2008) 7936.
[32] B. Chen, S. Ma, F. Zapata, F.R. Fronczek, E.B. Lobkovsky, H.-C. Zhou, Inorg. Chem.
46 (2007) 1233.
CCDC 759579, 759580, and 759581 contain the supplementary
crystallographic data for compound 1, 2, and 3, respectively for this
paper. These materials can be obtained free of charge from the
Cambridge crystallographic data centre via www.ccdc.cam.ac.uk/
conts/retrieving.html (or from the Cambridge Crystallographic
data centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44
1223336033).
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.molstruc.2010.02.019.
[33] D. Tanaka, K. Nakagawa, M. Higuchi, S. Horike, Y. Kubota, T.C. Kobayashi, M.
Takata, S. Kitagawa, Angew. Chem. Int. Ed. 47 (2008) 3914.
[34] G. Férey, Chem. Soc. Rev. 37 (2008) 191.
[35] M.-L. Zhang, D.-S. Li, J.-J. Wang, F. Fu, M. Du, K. Zou, X.-M. Gao, Dalton Trans.
(2009) 5355.
[36] B.-L. Chen, N.W. Ockwig, A.R. Millward, D.S. Contreras, O.M. Yaghi, Angew.
Chem. Int. Ed. 44 (2005) 4745.
[37] A.L. Grzesiak, F.J. Uribe, N.W. Ockwig, O.M. Yaghi, A.J. Matzger, Angew. Chem.
Int. Ed. 45 (2006) 2553.
[38] S.A. Bourne, J. Lu, A. Mondal, B. Moulton, M.J. Zaworotko, Angew. Chem. Int. Ed.
40 (2001) 2111.
[39] C. Livage, N. Guillou, J. Chaigneau, P. Rabu, M. Drillon, G. Férey, Angew. Chem.
Int. Ed. 44 (2005) 6488.
[40] Y.-F. Zhou, F.-L. Jiang, D.-Q. Yuan, B.-L. Wu, R.-H. Wang, Z.-Z. Lin, M.-C. Hong,
Angew. Chem. Int. Ed. 43 (2004) 5665.
[41] D.-R. Xiao, E.-B. Wang, H.-Y. An, Y.-G. Li, Z.-M. Su, C.-Y. Sun, Chem. Eur. J. 12
(2006) 6528.
[42] SMART & SAINT, Versions 6.22a; Bruker AXS: Madison, WI, 1999.
[43] G.M. Sheldrick, SADABS user guide, University of Göttingen, Germany, 1993.
[44] A. Altomare, G. Cascarano, C. Giacovazzo, A. Gualaradi, J. Appl. Crystallogr. 26
(1993) 343.
[45] G.M. Sheldrick, SHELXL 97 program for the solution of crystal structure,
University of Gottingen, Germany, 1997.
[46] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7.
[47] G.M. Sheldrick, SHELXS 97, program for the solution of crystal structure,
University of Gottingen, Germany, 1997.
References
[1] N. Guillou, P.M. Forster, Q. Gao, J.S. Chang, M. Nogues, S.-E. Park, A.K.
Cheetham, G. Férey, Angew. Chem. Int. Ed. 40 (2001) 2831.
[2] S. Horike, M. Dinca, K. Tamaki, J.R. Long, J. Am. Chem. Soc. 130 (2008) 5854.
[3] S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita, S.
Kitagawa, J. Am. Chem. Soc. 129 (2007) 2607.
[4] D.N. Dybtsev, A.L. Nuzhdin, H. Chun, K.P. Bryliakov, E.P. Talsi, V.P. Fedin, K. Kim,
Angew. Chem. Int. Ed. 45 (2006) 916.
[5] J.L.C. Rowsell, O.M. Yaghi, Angew. Chem. Int. Ed. 44 (2005) 4670.
[6] X. Lin, J. Jia, X. Zhao, K.M. Thomas, A.J. Blake, G.S. Walker, N.R. Champness, P.
Hubberstey, M. Schroder, Angew. Chem. Int. Ed. 45 (2006) 7358.
[7] R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R.V. Belosludov, T.C. Kobayashi,
H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita, Nature 436 (2005) 238.
[8] G. Li, W. Yu, J. Ni, T. Liu, Y. Liu, E. Sheng, Y. Cui, Angew. Chem. Int. Ed. 47 (2008)
1245.
[9] L. Pan, D.H. Olson, L.R. Ciemnolonski, R. Heddy, J. Li, Angew. Chem., Int. Ed. 45
(2006) 616.
[10] B. Chen, C. Liang, J. Yang, D.S. Contreas, Y.L. Clancy, E.B. Lobkovsky, O.M. Yaghi,
S. Dai, Angew. Chem. Int. Ed. 45 (2006) 1390.
[11] T.K. Maji, R. Matsuda, S. Kitagawa, Nat. Mater. 6 (2007) 142.
[12] B. Chen, Y. Ji, M. Xue, F.R. Fronczek, E.J. Hurtado, J.U. Mondal, C. Liang, S. Dai,
Inorg. Chem. 47 (2008) 5543.
[13] A.K. Cheetham, C.N.R. Rao, R.K. Feller, Chem. Commun. (2006) 4780.
[14] D. Bradshaw, J.B. Claridge, E.J. Cussen, T.J. Prior, M.J. Rosseinsky, Acc. Chem.
Res. 38 (2005) 273.
[48] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.
[15] C.N.R. Rao, S. Natarajan, R. Vaidhyanathan, Angew. Chem. Int. Ed. 43(2004)1466.