Use of different unsaturated dicarboxylates toward the design of new 3D and 2D networks of copper(II)

Article abstract of DOI:10.1002/ejic.200400328

Two new polymeric complexes of copper(II), [Cu(L1)(μ-fum)(μ-H ₂O)]_n (1) (fum = fumarate dianion; L1 = N,N′-dimethylethane-1,2-diamine) and [Cu(L2)(μ-tp)]_n (2) [tp = terephthalate dianion; L2 = N-(2-aminoethyl)-3-amino-1-propanol], have been synthesized. The molecular structures are determined by X-ray crystallography. Complex 1 is a fumarato-bridged zig-zag 1D chain of Cu^II-L1, which is extended to a 3D coordination polymer through bridging water molecules. Complex 2 is a chain of Cu^II in which the terephthalate anions bridge in alternate bis(bidentate) and bis-(monodentate) fashions. The coexistence of such types of bridging modes of terephthalate ions in a single molecule is unprecedented. The chelating terephthalate ion is linked to an equatorial and an axial site of consecutive metal ions, while the other terephthalate ion is axially linked to Cu^II centers. Both the complexes are characterized by variable-temperature susceptibility measurements at room temperature down to 4 K. Fitting of the magnetic data reveals the existence of weak antiferromagnetic interactions through the bridging dicarboxylate pathways. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Full text of DOI:10.1002/ejic.200400328

FULL PAPER
Use of Different Unsaturated Dicarboxylates Toward the Design of New 3D
and 2D Networks of Copper(II
)
Partha Sarathi Mukherjee,[a] Debajyoti Ghoshal,[a] Ennio Zangrando,*[b] Talal Mallah,[c] and
Nirmalendu Ray Chaudhuri*[a]
Keywords: Coordination polymers / Copper / Magnetic properties / Weak interaction / Dicarboxylate ligands
Two new polymeric complexes of copper(II), [Cu(L1)(µ-
fum)(µ-H2O)]n (1) (fum = fumarate dianion; L1 = N,NЈ-di-
bridging modes of terephthalate ions in a single molecule is
unprecedented. The chelating terephthalate ion is linked to
an equatorial and an axial site of consecutive metal ions,
methylethane-1,2-diamine) and [Cu(L2)(µ-tp)]n (2) [tp
=
terephthalate dianion; L2 = N-(2-aminoethyl)-3-amino-1-pro- while the other terephthalate ion is axially linked to CuII cen-
panol], have been synthesized. The molecular structures
are determined by X-ray crystallography. Complex 1 is a
fumarato-bridged zig-zag 1D chain of CuII−L1, which is ex- down to 4 K. Fitting of the magnetic data reveals the exist-
ters. Both the complexes are characterized by variable-tem-
perature susceptibility measurements at room temperature
tended to a 3D coordination polymer through bridging water
molecules. Complex 2 is a chain of CuII in which the tereph-
thalate anions bridge in alternate bis(bidentate) and bis-
ence of weak antiferromagnetic interactions through the
bridging dicarboxylate pathways.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
(monodentate) fashions. The coexistence of such types of Germany, 2004)
Introduction
supramolecular networks and look for molecular features,
such as functional groups, that can interfere and modify the
arrangements of molecules in crystals, a task that remains
a considerable challenge at present.
Construction of molecules with covalent and noncovalent
motifs has recently become a rapidly growing area of re-
search as it pursues to establish principles that will ulti-
mately lead to the development of new state-of-the-art
functional materials.[1Ϫ6] Among the noncovalent motifs,
hydrogen bonding[2,3] and π-π stacking[7] have been em-
ployed as synthetic paradigms to rationally design super-
structures. Recent progress in this area has generated ex-
amples in which the design of network structures has pro-
duced crystals with (a) one-dimensional (1D) molecular
networks composed of hydrogen bonding,[8,9] metalϪligand
coordination,[10,11] or a combination of these and other in-
teractions, referred to as hybrid interactions;[12] (b) 2D net-
Recently, di- and polycarboxylates have become one of
the most demanding spacers to the material chemist, and
especially to the inorganic chemist, for the synthesis of com-
pounds that have potential useful applications as molecular-
based magnetic materials as well as materials that mimick
zeolite with host-guest behavior.[17Ϫ19] Different types of di-
carboxylates like terephthalate, malonate, succinate, and
oxalates are widely used by these chemists, but use of fum-
arate is relatively less frequent due to poor solubility of its
coordination complexes in common solvents. We have re-
ported a new method of crystallization of CuII complexes
of fumarate that uses ammonia as solvent.[20] With this pro-
cedure we have already obtained and reported on some
interesting molecular architectures.[20,21] We are currently
exploring the design of molecules that use suitable metal
ions and ligands capable of forming H-bonds as well as π-
π interactions as directional motifs to extend the dimen-
sionality of the molecule. The present article contributes to
the synthesis, crystal structure, and variable-temperature
magnetic behavior of two CuII complexes with unsaturated
dicarboxylate as bridging ligands, namely [Cu(L1)(µ-
fum)(µ-H2O)]n (1) and [Cu(L2)(µ-tp)]n (2) [fum ϭ fumarate
dianion; tp ϭ terephthalate dianion; L1 ϭ N,NЈ-dimethyl-
ethane-1,2-diamine; L2 ϭ N-(2-aminoethyl)-3-amino-1-pro-
works
comprising
either
hydrogen
bonding[13]
/
metalϪligand coordination[14] or hybrid interactions; and
(c) 3D networks composed of hydrogen bonding[15] or
metalϪligand coordination.[16] These approaches seek to
establish structural relationships between the molecular and
[a]
Department of Inorganic Chemistry, Indian Association for the
Cultivation of Science,
Jadavpur, Kolkata 700032, India
Fax: (internat.) ϩ 91-33-24732805
E-mail: icnrc@iacs.res.in
[b]
Dipartimento di Scienze Chimiche, University of Trieste,
34127 Trieste, Italy
[c]
Laboratoire de Chimie Inorganique, UMR CNRS 8613,
Universite de Paris-Sud, 91405 Orsay, France
Eur. J. Inorg. Chem. 2004, 4675Ϫ4680
DOI: 10.1002/ejic.200400328
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4675

P. S. Mukherjee, D. Ghoshal, E. Zangrando, T. Mallah, N. Ray Chaudhuri
˚
FULL PAPER
panol]. The results of the structural analysis of complex 1 [2.481(2) A]. A selection of bond lengths and angles is re-
reveals a 3D network and that of 2 a chain with alternating ported in Table 1. The dicarboxylate anion spans the metal
˚
bis(bidentate) and bis(monodentate) bridging modes of atoms with a distance of 8.857 A, a distance similar to those
˚
terephthalate, which results in a molecule with a unique of 8.653 and 8.666 A observed in two dinuclear fumarate-
topology. The coexistence of terephthalate ligands with dif- bridged CuII complexes.[22,23] It is worthwhile to note the
ferent bridging fashions inside a single molecule has not
been reported earlier. These unsaturated dicarboxylates
are chosen as spacers because of the following reasons: (i)
fumarate and terephthalate show versatile coordination
modes (Scheme 1); (ii) they coordinate metal ions to form
unidimensional coordination chains, which, in general, can
enlarge the dimensionality through H-bonding; and (iii)
they have ethylenic and phenyl moieties that are capable of
forming π-π stacking as a directional motif (Scheme 2).
Figure 1. ORTEP drawing (thermal ellipsoid at 40% probability
level) of the polymeric arrangement of 1 with atom labeling
scheme; dotted lines indicate intrachain H-bonds
˚
Table 1. Selected bond lengths [A] and angles [°] for complex
[Cu(L1)(µ-fum)(µ-H2O)] (1)
Scheme 1. [X ϭ ϪCHϭCHϪ or ϪC6H4Ϫ (1,4)]
CuϪO(2)
CuϪN(1)
CuϪO(1)
1.973(2) O(2)ϪC(3)
2.022(2) O(3)ϪC(3)
2.481(2) C(4)ϪC(4ЈЈ)[a]
1.265(3)
1.234(3)
1.311(5)
85.4(1)
90.13(8)
86.54(8)
87.9(1)
O(2)ϪCuϪN(1Ј)[a] 174.88(8)
N(1Ј)ϪCuϪN(1)
N(1)ϪCuϪO(1)
N(1)ϪCuϪO(1Ј)
O(2)ϪCuϪO(2Ј)
C(3)ϪO(2)ϪCu
O(2)ϪCuϪN(1)
O(2)ϪCuϪO(1)
O(2)ϪCuϪO(1Ј)
O(1Ј)ϪCuϪO(1)
93.60(9)
98.48(7)
84.80(7)
175.5(2)
123.3(2)
[a]
Symmetry operations: (Ј): 1.25 Ϫ x, 0.25 Ϫ y, z; (ЈЈ): 1 Ϫ x, Ϫy,
1 Ϫ z.
Scheme 2. Possible sites for coordination as well as supramolecular
interaction in terephthalate (a) and fumarate (b)
Results and Discussion
Description of the Structures
[Cu(L1)(µ-fum)(µ-H2O)]n (1)
The crystal structure of 1 consists of CuII(L1) units con-
nected through bridging amphi-monodentate fumarate di-
anions to form polymeric chains with a zig-zag arrange-
ment (Figure 1). Each copper atom is located on a twofold
crystallographic axis with an elongated octahedral ge-
ometry that involves the diamine ligand donors N(1) and
the carboxylic oxygen atom O(2) in the equatorial positions,
and two water molecules as axial ligands. The former dis-
˚
tances [CuϪO(2) 1.973(2), CuϪN(1) 2.022(2) A] are signifi-
Figure 2. Perspective view of the packing of 1 showing the inter-
cantly shorter than those involving the water molecule secting Cu(L1)(fum) chains (water molecules not shown for clarity)
4676  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4675Ϫ4680

Design of New 3D and 2D Networks of Copper(II)
FULL PAPER
packing shown by the X-ray structural analysis, in which bis(bidentate) terephthalate. The respective intramolecular
the coordination polymers present an intersecting arrange- CuϪCu distances spanned by the anions are 10.998(5) and
˚
ment (Figure 2). The dimensionality of the network is en- 10.830(3) A; the small difference appears to be caused by
larged to 3D through the axially coordinated water mol- the ligand coordination mode. In fact, making allowance
ecules that bridge consecutive metal ions as depicted in Fig- for packing and for the different ligands bound at the metal
˚
ure 3. These Ϫ(CuϪH2O)nϪ chains are characterized by a atom, distances of about 11.0 A were found for copper ions
metalϪmetal separation of 4.512 A and a CuϪOH2ϪCuЈЈ bridged by bis(monodentate) terephthalate anions,[24Ϫ26]
˚
˚
bond angle of 130.6(1)°. The dicarboxylate skeleton is not while
a
separation of 10.710
A
was reported in
coplanar, and instead, a O(3)ϪC(3)ϪC(4)ϪC(4ЈЈ) torsion [(CuL")2tp](ClO4)2 (L" ϭ pentaethyldiethylenetriamine)[27]
angle of 145.0(4)° is observed. This conformational feature in which the anion bridges in a chelating bis(bidentate)
is likely assumed in order to favor the intrachain H-bond fashion. The carboxylate group C(6)/O(2)/O(3) is nearly co-
formation between the coordinated water molecule and the planar with the phenyl ring [4.9(3)°], while C(10)/O(4)/O(5)
fumarate oxygen atom O(3) (Figure 3; OϪO 2.651 A). exhibits a tilt of 24.0(5)°. This dihedral angle was tentatively
However, the C(4)ϪC(4ЈЈ) bond length of 1.311(5) A still taken into account to assess the magnetic exchange coup-
˚
˚
indicates a larger double-bond character relative to that of ling with structural parameters in transition metal ions
˚
the C(3)ϪC(4) bond [1.491(3) A].
bridged by a tp ligand.[28] The described polymers are held
together through strong hydrogen bonds that occur between
the hydroxy group O(1)ϪH and the carboxylate oxygen
˚
atom O(5) [2.678 A, O(1)ϪH···O(5) 159.07°] to yield a lay-
ered structure (Figure 5) in which the shortest interchain
˚
CuϪCu distance is 5.532(1) A. Moreover, the phenyl groups
of the bis(bidentate) terephthalate are not coplanar with
Figure 3. Bridging water molecules connecting the coordination
polymers to form a 3D network in 1; dotted lines indicate H-bonds
[O(3Ј) at 1.75 Ϫ x, y, 0.75 Ϫ z; CuЈЈ at 0.5 ϩ x, 0.25 Ϫ y, 0.75 Ϫ z]
[Cu(L2)(µ-tp)]n (2)
The structure of complex 2 consists of 1D polymeric
chains formed by Cu(L2) moieties [L2 ϭ N-(2-aminoethyl)-
3-amino-1-propanol] bridged by terephthalate anions. The
polymeric motifs, together with the atom numbering
scheme, is shown in Figure 4, and a selection of bond
lengths and angles is given in Table 2. The metal environ-
ment can be described as a distorted octahedron in which
the equatorial positions are occupied by the hydroxy-di-
amine ligand donors and by the carboxyl oxygen atom
O(2), while the oxygen atoms O(4) and O(3) of different
bridging terephthalate anions complete the coordination
sphere. The latter distances [CuϪO(4) 2.300(4), CuϪO(3)
Figure 4. ORTEP drawing (thermal ellipsoid drawn at 40% prob-
ability level) of the polymeric chain of 2 with atom labeling scheme;
the broken lines indicate the weak interaction between the copper
and carboxyl oxygen O(3) atoms
˚
2.553(4) A] are significantly longer with respect to those in
˚
the basal plane [range 1.971(4)Ϫ2.027(5) A]. The distor-
˚
Table 2. Selected bond lengths [A] and angles [°] of [Cu(L2)-
tions from the octahedral geometry are indicated by the
small bite angle of the carboxylate group O(2)ϪCuϪO(3)
[56.7(2)°] and by the O(4)ϪCuϪO(3) angle [153.3(1)°]. The
(µ-tp)] (2)
CuϪO(1)
CuϪO(2)
CuϪN(1)
2.006(4)
1.971(4)
1.997(5)
2.027(5)
2.553(4)
89.4(2)
172.6(2)
89.2(2)
82.6(2)
90.5(2)
95.7(2)
165.7(2)
56.7(2)
97.7(2)
CuϪO(4)
O(2)ϪC(6)
O(3)ϪC(6)
O(4)ϪC(10)
2.300(4)
1.273(7)
1.231(7)
1.265(7)
1.246(7)
84.6(2)
˚
four equatorial donors are coplanar Ϯ0.086(3) A, with the
˚
metal atom slightly displaced by 0.164(3) A from their
mean plane towards O(4). Thus, along the chain, two CuϪN(2)
terephthalate anions, both having the phenyl ring located
CuϪO(3)
O(1)ϪCuϪO(2)
O(5)ϪC(10)
N(1)ϪCuϪN(2)
N(1)ϪCuϪO(3)
N(1)ϪCuϪO(4)
N(2)ϪCuϪO(3)
N(2)ϪCuϪO(4)
O(4)ϪCuϪO(3)
C(10)ϪO(4)ϪCu
C(6)ϪO(2)ϪCu
C(6)ϪO(3)ϪCu
about a crystallographic symmetry center, connect Cu(L2)
units, alternatively in a bis(monodentate) and a chelating
bis(bidentate) fashion (Figure 4). The simultaneous pres-
ence of terephthalate ligands with different bridging fa-
shions gives rise to an unprecedented coordination chain.
The dihedral angle formed by the anions with the equa-
torial coordination plane is 45.9(1) and 80.3(2)°, the latter
indicating a nearly perpendicular orientation for the
O(1)ϪCuϪN(1)
O(1)ϪCuϪN(2)
O(1)ϪCuϪO(3)
O(1)ϪCuϪO(4)
O(2)ϪCuϪN(1)
O(2)ϪCuϪN(2)
O(2)ϪCuϪO(3)
O(2)ϪCuϪO(4)
95.7(2)
94.1(2)
109.1(2)
96.4(2)
153.3(1)
128.7(4)
102.8(4)
76.9(3)
Eur. J. Inorg. Chem. 2004, 4675Ϫ4680
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4677

P. S. Mukherjee, D. Ghoshal, E. Zangrando, T. Mallah, N. Ray Chaudhuri
FULL PAPER
aromatic rings of neighboring chains, but are perpendicular.
As a consequence, the phenyl centroid of the latter is at a
˚
distance of 2.66 A from the HϪC group of the adjacent
aromatic ring leading to a CϪH···π interaction (Figure 5).
Figure 6. Plot of χMT vs. T (squares) and χM vs. T (circles) data;
solid lines show the best fit obtained considering a uniform chain
of S ϭ 1/2 local spin states
Figure 5. Perspective view of the layered structure in 2 (along axis
a) showing the interchain H-bonding scheme and the CϪH···π in-
teractions
[Cu(L2)(µ-tp)] (2)
Magnetic Properties
The structural analysis reveals a 1D chain with dicar-
boxylate anions in a different alternating bridging mode.
We have considered that an axialϪaxial bridging tereph-
thalate ion has no influence on magnetic coupling since the
unpaired electron on the CuII atom is not concentrated in
axial orbital regions. The χMT vs. T plot shows a gradual
decrease in χMT values with decreasing temperature (Fig-
ure 7), which indicates the existence of antiferromagnetic
interactions within the complex. The χMT vs. T data are
fitted using the BleaneyϪBowers formula[29] of the CuII lo-
[Cu(L1)(µ-fum)(µ-H2O)]n (1)
The magnetic behavior of complex 1 was investigated
using a SQUID magnetometer in the temperature region
280Ϫ4 K within an applied magnetic field of 5 kOe. The
χMT product first decreases smoothly and then abruptly
when cooling down from T ϭ 280 K. It reaches a value
close to zero at T ϭ 4 K. The χM ϭ f(T) plot is shown in
Figure 6. These magnetic data are consistent with the pres-
ence of a weak antiferromagnetic interaction between the
CuII ions within the compound even though the shorter
cal spin state. The results of the best fit are J ϭ Ϫ6 cmϪ1
,
ρ ϭ 0.007, g ϭ 2.01, R ϭ 1.8·10Ϫ5, which are similar to
those previously reported for a similar type of bridging tp
core.[25]
˚
CuϪCu distance is larger than 6 A. The susceptibility data,
using the 1D chain model of the CuII system, was fitted,
resulting in a J value of Ϫ2.6 cmϪ1. This value is satisfac-
tory, since it is of the same order of magnitude as that from
a previously reported communication in which a 3D inter-
locked network of CuII ions has a bridging fumarate ion
that is linked in a similar manner to that in the present
complex.[21] From a structural point of view, each copper
atom, located on a twofold crystallographic axis, shows an
elongated octahedral geometry involving the diamine ligand
donors and a carboxylic oxygen atom in the equatorial po-
sitions, and two water molecules at the axial sites. Due to
this axially elongated geometry of CuII centers, the magneti-
cally active unpaired electron on each CuII atom is located
2
2
2
on the basal dx Ϫy orbital, whereas the dz orbital is occu-
pied by paired electrons. Since each bridging water is bound
2
to the dz (nonmagnetic) orbital of two CuII centers, the
coupling interaction through the aqua bridging pathway
may be considered to be zero. Therefore, in the fitting, we
did not consider the coupling interaction through the water
bridging pathway, and rather, for magnetic study, the com-
pound was considered as a 1D coordination chain.
Figure 7. Fitting of χMT vs. T data using the dimeric model of S ϭ
1/2 local spins; solid line shows the best fit obtained
4678
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 4675Ϫ4680

Design of New 3D and 2D Networks of Copper(II)
FULL PAPER
Conclusions
with an EnrafϪNonius MACH 3 and a CAD4 EnrafϪNonius
single-crystal diffractometer, respectively, equipped with a graphite
˚
monochromator and Mo-Kα radiation (λ ϭ 0.71073 A). Three
This article presents the synthesis, single-crystal struc-
ture, and magnetic behavior of two dicarboxylate-bridged
metal complexes. Complex 1 is a 3D network of CuII in
which both a fumarate ion and a water molecule function
as a bridging ligand. CuϪfumarate zig-zag chains are in-
volved in the bridging by water molecules to form a 3D
network. On the other hand, complex 2 is a 1D chain of
CuIIϪterephthalate in which the dicarboxylate is alternately
bridged in a bis(bidentate) and a bis(monodentate) fashion
in an axialϪaxial and equatorialϪequatorial mode to form
a unique molecule since such an alternate coordination fa-
shion has not been reported earlier for terephthalate sys-
tems. Furthermore, the solid-state structure of complex 2
is stabilized by CϪH···π interactions. Here, the role of the
chemically different dicarboxylates upon the formation of
the superstructure is a crucial aspect open to theoretical
speculations. Low-temperature magnetic susceptibility data
standard reflections, measured at regular intervals throughout the
data collection, showed no noticeable variation in intensity. An ab-
sorption correction based on the ψ-scan method was applied (max./
min. T ϭ 0.9988/0.8316 for 1 and 0.9971/0.8035 for 2). The struc-
ture was solved by conventional Patterson and Fourier analyses
and refined on F2 by full-matrix anisotropic least-squares method
using the SHELXL-97 package.[30] All the calculations were per-
formed using the WinGX System, Ver 1.63.[31] Crystal data and
refinement details are given in Table 3. X-ray crystallographic data
in CIF format for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data Centre.
CCDC-236904 and -236905 contain these data, which 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].
1
of 1 were fitted to the equation of a chain of S ϭ /2 local
spins, which reveal the existence of weak antiferromagnetic
interactions along the fumarate pathway. In the case of 2,
the variable-temperature magnetic data were fitted to a di-
Table 3. Crystal data and structure refinement for complexes
[Cu(L1)(µ-fum)(µ-H2O)] (1) and [Cu(L2)(µ-tp)] (2)
1
1
2
meric formula of S ϭ /2 spin state, which indicates a weak
antiferromagnetic interaction along the terephthalate path-
way.
Empirical formula
M
C8H16CuN2O5
283.77
C13H18CuN2O5
345.83
T [K]
293(2)
293(2)
monoclinic
P21/n
7.437(3)
9.367(2)
20.103(5)
94.07(4)
1396.8(7)
4
Crystal system
Space group
orthorhombic
Fddd (choice 2)
9.016(4)
16.322(6)
30.908(8)
90.00
4548(4)
16
1.685
˚
a [A]
Experimental Section
˚
b [A]
˚
c [A]
Synthesis of Cu(L1)(µ-fum)(µ-H2O)] (1): 1 mmol of N,NЈ-dimethyl-
ethane-1,2-diamine was slowly added drop by drop to an aqueous
solution of CuCl2·2H2O (5 mL, 1 mmol, 0.1705 g), resulting in a
deep blue solution. An aqueous solution of Na2Ϫfumarate (10 mL,
1 mmol, 0.160 g) was added with continuous stirring and the stir-
ring continued for 40 min and then filtered. Suitable blue single
crystals for X-ray analysis were obtained after 15 d on keeping the
deep blue filtrate in a refrigerator. C8H16CuN2O5 (283.77): calcd.
C 33.80, H 5.63, N 9.86; found C 32.17, H 5.73, N 10.14. IR:
ν(COOϪ) ϭ 1392, 1562 cmϪ1; ν(NϪH) ϭ 3000 cmϪ1; ν(OϪH) ϭ
β [°]
3
˚
V [A ]
Z
Dcalcd. [g cmϪ1
]
1.644
1.587
µ(Mo-Kα) [mmϪ1
]
1.929
Reflections collected
4929
1316
0.0689
0.0322
0.0720
1.016
0.281/Ϫ0.427
4307
3976
0.0638
0.0633
0.1709
1.207
1.483/Ϫ0.742
Unique reflections
R(int)[a]
R1
wR2
GOF
Residuals [e·A
3450Ϫ3370 cmϪ1
.
Ϫ3
˚
]
Synthesis of [Cu(L2)(µ-tp)] (2): A methanolic solution of a mixture
of terephthalic acid (1 mmol) and triethylamine (2 mmol) was lay-
ered on a blue aqueous solution of Cu(ClO4)2·6H2O (1 mmol) and
N-(2-aminoethyl)-3-amino-1-propanol (1 mmol). After a month, a
microcrystalline blue complex with suitable single crystals for X-ray
diffraction were obtained. The crystals were separated by a needle.
C13H18CuN2O5 (345.83): calcd. C 45.10, H 5.20, N 8.09; found C
[a]
2
2 2
2 2
R ϭ ||Fo| Ϫ |Fc||/|Fo|; Rw ϭ {[w(Fo Ϫ Fc ) ]/[w(Fo ) ]}1/2
.
Acknowledgments
Funding for the work described here was provided by the Council
of Scientific and Industrial Research, New Delhi (grant to NRC),
and they are gratefully acknowledged. We also thank Dr. S. Pal,
School of Chemistry, University of Hyderabad, India for X-ray
data collection.
44.87, H 5.33, N 9.84. IR: ν(COOϪ) ϭ 1372, 1543 cmϪ1
ν(NϪH) ϭ 3050 cmϪ1; ν(OϪH) ϭ 3400Ϫ3350 cmϪ1
;
.
Physical Measurements: IR spectra were recorded with a Nicolet
520 FTIR spectrometer using KBr pellets. Magnetic measurements
were carried out on a polycrystalline sample with a SQUID mag-
netometer operating in the 2Ϫ300 K temperature range with an
applied field of 5 kOe. Diamagnetic corrections were estimated
from Pascal constants.
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