One-dimensional and two-dimensional coordination polymers of copper(II) nitrobenzoate with bridging 3-pyridylmethanol ligand

Article abstract of DOI:10.1002/zaac.200900356

Complexes of composition [Cu(X-NO₂bz)₂(μ-3PM) ₂]_n [X-NO₂bz = 2-nitrobenzoate (1), 3-nitrobenzoate (2) or 4-nitrobenzoate (3) and 3PM. = 3-pyridylmethanol] were prepared and studied by elemental, analysis, UV/Vis, IR and. EPR spectroscopy. The molecular structures of two new complexes 1 and 3 were solved. The copper atoms of both complexes exhibit an elongated octahedral coordination environment with the equatorial positions occupied by two monoden-tate nitrobenzoato anions and two 3-pyridylmethanol nitrogen atoms in trans positions. The both, axial positions are occupied by oxygen atoms of bridging 3-pyridylmetanol ligands The polymeric structure of complex [Cu(2-NO₂bz)₂(μ-3PM) ₂]., (1) contains two-dimensional layers. The complex 3 exhibits a polymeric chain-like structure [Cu(4NO₂bz)₂(μ-3PM) ₂]_n with copper atoms double-bridged by two 3-pyridylmethanol molecules similarly as it was found for complex 2.

Full text of DOI:10.1002/zaac.200900356

ARTICLE
DOI: 10.1002/zaac.200900356
One-Dimensional and Two-Dimensional Coordination Polymers of
Copper(II) Nitrobenzoate with Bridging 3-Pyridylmethanol Ligand
Jana Kavalírová,[a] Zuzana Vasková,[a] Jaroslava Maroszová,[a] Jan Moncol,*[a]
Marian Koman,[a] Tadeusz Lis,[b] Milan Mazur,[c] and Dušan Valigura[a]
Keywords: Copper; Solid-state structures; Coordination polymers; Bridging ligands; Metal-organic frameworks
Abstract. Complexes of composition [Cu(X-NO2bz)2(μ-3PM)2]n tate nitrobenzoato anions and two 3-pyridylmethanol nitrogen atoms
[X-NO2bz = 2-nitrobenzoate (1), 3-nitrobenzoate (2) or 4-nitrobenzoate in trans positions. The both axial positions are occupied by oxygen
(3) and 3PM = 3-pyridylmethanol] were prepared and studied by ele- atoms of bridging 3-pyridylmetanol ligands The polymeric structure of
mental analysis, UV/Vis, IR and EPR spectroscopy. The molecular complex [Cu(2-NO2bz)2(μ-3PM)2]n (1) contains two-dimensional lay-
structures of two new complexes 1 and 3 were solved. The copper ers. The complex 3 exhibits a polymeric chain-like structure [Cu(4-
atoms of both complexes exhibit an elongated octahedral coordination NO2bz)2(μ-3PM)2]n with copper atoms double-bridged by two 3-pyri-
environment with the equatorial positions occupied by two monoden- dylmethanol molecules similarly as it was found for complex 2.
plexes with 3-pyridylmethanol as terminal ligand exist. For ex-
ample, the complex [Cu2(CH3CO2)4(3PM)2]·CH2Cl2 has a pad-
Introduction
The field of coordination polymers represents growing area
of solid-state coordination chemistry and crystal engineering [1,
2]. Metal-organic frameworks with flexible or rigid micropo-
rous channels are interesting materials with useful properties as
physical adsorption of gas [3], heterogeneous catalysis [4], non-
liner optical materials [5], luminescent materials [6], dynamic
porous coordination polymers [7] and magnetic materials [8].
The compound 3-pyridylmethanol can be used as flexible
bridging ligand [9] for construction of metal-organic frame-
works [10]. It is well known that the ligand usually prefers
formation of carboxylato copper(II) complexes with
[Cu(RCO2)2(μ-3PM)2]n stoichiometry. The structures of the
complexes are one-dimensional chain-like [10–14], or two-di-
mensional sheet-like [10, 15–20]. The similar one-dimensional
chain-like structures were found for carboxylato zinc(II) [21]
and for carboxylato cadmium(II) [22] complexes. On the other
hand, only a few dinuclear and mononuclear copper(II) com-
dle-wheel dinuclear molecular structure with two terminal
3-pyridylmethanol ligands [23]. The carboxylato copper(II)
complexes [Cu(2-NO2bz)2(3PM)2-(H2O)2] [11] and [Cu(3-
pyac)2(3PM)2(H2O)] (3-pyac = 3-pyridylacrylato) [24] exhibit
monomeric molecular structures with two terminal 3-pyridyl-
methanol ligands. Terminal 3-pyridylmethanol ligands were
also found in the mononuclear complex [CuCl2(3PM)4] [25]
and in the oxalato-bridged coordination polymer [Cu(μ-
C2O4)(3PM)2]n [26] as well as in some iron(III) [27], cad-
mium(II) [28], zinc(II) [29] and platinum(II) [30, 31] com-
plexes. Two other copper(II) coordination polymers
[Cu3(C2H5CO2)6(μ-3PM)2(3PM)2]n [32] and [Cu3(2-Clnic)6-
(μ-3PM)4(3PM)2]n (2-Clnic = 2-chlornicotinato) [10] are
known in which the 3-pyridylmethanol molecules act as bridg-
ing as well as terminal ligands.
In this report, we describe the synthesis and spectral proper-
ties of coordination polymers: [Cu(2-NO2bz)2(μ-3PM)2]n (1),
[Cu(3-NO2bz)2(μ-3PM)2]n (2) and [Cu(4-NO2bz)2(μ-3PM)2]n
(3), where 2-NO2bz = 2-nitrobenzoate; 3-NO2bz = 3-nitroben-
zoate; 4-NO2bz = 4-nitrobenzoate and 3PM = 3-pyridylmetha-
nol. The molecular structure of [Cu(3-NO2bz)2(μ-3PM)2]n (2)
has been already published [13], but some new aspects of the
structure of compound 2 are presented herein together with its
spectral properties. Herein, we additionally present the molec-
ular structures of [Cu(2-NO2bz)2(μ-3PM)2]n (1) and [Cu(4-
NO2bz)2(μ-3PM)2]n (3).
* Dr. J. Moncol
Fax: +421-2524-93-198
E-Mail: jan.moncol@stuba.sk
[a] Department of Inorganic Chemistry
Slovak University of Technology
Radlinskeho 9
SK-812 37 Bratislava, Slovakia
[b] Faculty of Chemistry
University of Wrocław
14 Joliot-Curie St
50–383 Wrocław, Poland
[c] Department of Physical Chemistry
Slovak University of Technology
Radlinskeho 9
Results and Discussion
[Cu(2-NO2bz)2(μ-3PM)2]n (1)
SK-812 37 Bratislava, Slovakia
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.200900356 or from the
author.
The molecular structure of compound 1 contains two-dimen-
sional sheets parallel to the ab plane. Each Cu2+ cation is lo-
Z. Anorg. Allg. Chem. 2010, 636, 589–594
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
589

J. Moncol et al.
ARTICLE
Table 1. Selected bond lengths and hydrogen bond parameters /Å and °
for 1–3.
cated on an inversion center. The coordination environment
around the Cu2+ cation is square-bipyramidal (Figure 1). The
equatorial plane consists of a pair of monodentate 2-nitroben-
zoate ligands bound through their carboxylate oxygen atoms
[Cu–O1 = 1.965(1) Å] and a pair of neutral 3-pyridylmethanol
molecules coordinated through their pyridine nitrogen atoms
[Cu–N1 = 2.021(1) Å]. The axial positions are occupied by
two hydroxy oxygen atoms [Cu–O5i = Cu–O5ii = 2.472(1) Å,
symmetry code: (i) –x + 3/2, y – 1/2, z; (ii) x – 1/2, –y + 1/2,
–z + 1] from two adjacent symmetry-related 3-pyridylmethanol
molecules.
1
2
3
Cu–O1
1.965(1)
2.021(1)
2.472(1)
90.18(5)
1.986(1)
2.037(1)
2.372(1)
89.73(5)
86.47(5)
85.87(5)
1.973(2)
2.043(2)
2.475(2)
90.13(7)
85.25(7)
84.60(7)
Cu–N1
Cu–O5ax
O1–Cu–N1
O1–Cu–O5ax 87.54(5)
N1–Cu–O5ax 87.21(5)
Hydrogen
bond
O5–H5O···O2iii O5–H5O···O2vii O5–H5O···O2vii
H···A
1.93
1.81
1.83
D···A
2.726(2)
156
2.617(2)
162
2.628(3)
165
D–H···A
[this work]
[13]
[this work]
Symmetry code: (iii) –x + 3/2, y + 1/2, z; (vii) –x + 2, –y + 1, –z + 1.
Figure 1. Perspective view of [Cu(2-NO2bz)2(μ-3PM)2]n (1), with the
atom-numbering scheme. Thermal ellipsoids are drawn at the 30 %
probability level. [Symmetry code: (i) –x + 3/2, y – 1/2, z; (ii) x – 1/
2, –y + 1/2, –z + 1].
Figure 2. Crystal packing of two-dimensional coordination polymer
[Cu(2-NO2bz)2(μ-3PM)2]n (1).
The hydroxy hydrogen atoms of 3-pyridylmethanol are “fixed”
to the uncoordinated carboxylate oxygen atoms O2 by hydrogen
bonds O5–H5O···O2iii [symmetry code: (iii) –x
+ 3/2,
y + 1/2, z] with interatomic O5···O2 distances of 2.7259(17) Å
and six-membered metallocycles are created. Details of the hy-
drogen bonding parameters are given in Table 1. An additional
[Cu(4-NO2bz)2(μ-3PM)2]n (3)
The molecular structure of compound 3 with atomic-number-
π–π stacking interaction between the molecules of 1 [33] was ing scheme of independent part is shown in Figure 3. The in-
found between the centroids cg of two adjacent pyridine rings, dependent part of the molecule consists of the copper atom,
iv
N1/C8–C12 with cg···cg = 3.78 Å [symmetry code: (iv) –x + 1, which is bonded centrosymmetrically to two monodentate 4-
–y + 1, –z + 1]. The distance between parallel planes of stacked nitrobenzoato anions through the oxygen atoms O1 [Cu–O1 =
pyridine rings is 3.42 Å. Many complexes of [Cu(RCO2)2- 1.973(2) Å] and two 3-pyridylmethanol molecules bonded
(μ-3PM)2]n stoichiometry are two-dimensional coordination poly- through the pyridine nitrogen atoms N1 [Cu–N1
=
mers, but only the complex [Cu(sal)2(μ-3PM)2]n (sal = salicylato) 2.043(2) Å]. The coordination polyhedron of the copper atom
[18, 19] has shown a crystal structure similar to complex 1 (Fig- is completed by two oxygen atoms O4 of the neighboring 3-
ure 2). The crystal system of both complexes is orthorhombic in pyridylmethanol hydroxy groups [Cu–O5v = Cu–O5vi
=
space group Pbca. The crystal systems of the other two-dimen- 2.475(2) Å, symmetry code: (v) x – 1, y, z; (vi) –x + 2, –y +
sional coordination polymers [Cu(RCO2)2(μ-3PM)2]n (RCO2 = 1, –z + 1] giving the distorted octahedral arrangement. A pair
2-chlorobenzoato [10], 2,6-dimethoxynicotinato [15], 4-chlorosal- of 3-pyridylmethanol molecules bridge each pair of adjacent
icylato [16], flufenamato [17] or clofibrinato [20]) are monoclinic copper atoms (Figure 4, A) and an infinite linear chain of dou-
in space group P21/c.
bly bridged copper atoms is formed.
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Z. Anorg. Allg. Chem. 2010, 589–594

Coordination Polymers of Copper(II) Nitrobenzoate
a axis (Figure 4A). The angle between the plane of the major
part of the disordered nitro group and the plane of the benzene
ring of 4-nitrobenzoate is 9.3°. It is close to planarity and con-
curs that two 4-nitrobenzoate anions are stacked (see Support-
ing Information, Figure S1) by their 4-nitrophenyl groups. The
distance between two planes of stacked benzene rings of 4-
nitrobenzoate anions [C2–C7] amounts 3.53 Å and the cg···cg
distance is 3.93 Å. The stacked 4-nitrobenzoate anions are
linking the infinite by 3-pyridylmethanol doubly bridged
chains into two-dimensional supramolecular layers and the
copper atoms and stacked 4-nitrobenzoate anions are in linear
arrangement (Figure S1).
The molecular structure of complex 2 is similar to that of
complex 3 [13]; selected bond lengths and angles for compari-
son are given in Table 1. The crystal structure of 2 creates
infinite chains, which are collinear to the a axis (Figure 4, B).
The benzene rings together with nitro-groups of 3-nitrobenzo-
ate anions are stacked too (see supplementary Figure S1) and
layers create two-dimensional supramolecular frameworks.
The angle between the nitro group and the benzene ring of 3-
nitrobenzoate anion is 8.5°. The distance between the two
planes of benzene rings of 3-nitrobenzoate anions [C2–C7]
amounts 3.55 Å and the cg···cg distance is 4.08 Å. The stacked
3-nitrobenzoate anions are linking the infinite chains to two-
dimensional supramolecular layers, but the copper atoms and
stacked 3-nitrobenzoate anions are in zigzag arrangement (Fig-
ure S2). Similar stacked nitro-groups and benzene rings are
known for the crystal structure of [Cu(3,5-(NO2)2bz)2(μ-
3PM)2]n (3,5-(NO2)2bz = 3,5-dinitrobenzoate) [11], but in the
crystal structure of [Cu(2-MeSnic)2(μ-3PM)2]n (2-MeSnic = 2-
methytionicotinate) only π–π stacking interaction between pyr-
idine rings of 2-methyltionicotinate anions is observed [10].
Figure 3. Perspective view of [Cu(4-NO2bz)2(μ-3PM)2]n (3), with the
atom numbering scheme. Thermal ellipsoids are drawn at the 30 %
probability level. [Symmetry code: (v) x – 1, y, z; (vi) –x + 2, –y +
1, –z + 1].
Supramolecular Structure Comparison
As it was mentioned above, complex 1 builds up a two-di-
mensional coordination polymer whereas the other two “iso-
meric” complexes 2 and 3 construct one-dimensional poly-
mers. Moreover, another one-dimensional polymer [Cu(3,5-
(NO2)2bz)2(μ-3PM)2]n has been already published [11] to-
gether
with
the
monomeric
complex
[Cu(2-
NO2bz)2(3PM)2(H2O)2]. An interesting feature of the last men-
tioned complex is that taking into account the orientation of
the 3PM ligands the structure could be explained as one-di-
mensional doubly bridged chain (Figure S3) with metha-
nol···water O–H···OW hydrogen bridges. The insertion of water
molecules into the bridges increased the Cu···Cu distance to
9.312 Å, whereas the O–H···O hydrogen bond parameters
[O···OW distance 2.723(2) Å and O–H···OW angle 157°] are
Figure 4. Crystal packing of one-dimensional coordination polymer:
A) [Cu(4-NO2bz)2(μ-3PM)2]n (3) and B) [Cu(3-NO2bz)2(μ-3PM)2]n
(2).
The strong hydrogen bonds between each 3-pyridylmethanol very similar to those of 2 or 3. The comparison of the Cu···Cu
hydroxy group and the oxygen O5 atom of the coordinated distance within the group of 1D complexes (6.878(1) Å for
carboxylate group of the 4-nitrobenzoate anions (O2) by hy- 3, 6.692(1) Å for 2 and 7.618(2) Å for [Cu(3,5-(NO2)2bz)2(μ-
drogen bonds O5–H5O···O2vii [symmetry code: (vii) –x + 2, 3PM)2]n) shows great variation for complexes with the same
–y + 1, –z + 1] with interatomic distances O5···O2 of ligand 3PM. It is unexpectedly wide in comparison to the ac-
2.628(2) Å are formed and six-membered metallacyclic rings cording Cu–N or plane-to-plane distances between the pyridine
are created. Details of the hydrogen-bonding parameters are ring pairs (2.648 Å for 3, 2.667 Å for 2 and 2.642 Å for
given in Table 1. The infinite chains of 3 are collinear to the [Cu(3,5-(NO2)2bz)2(μ-3PM)2]n) and is caused by free rotation
Z. Anorg. Allg. Chem. 2010, 589–594
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591

J. Moncol et al.
ARTICLE
of–CH2OH arm. Positioning of –CH2OH relative to the pyri- otinamide) exhibit greater variability in composition, structure
dine ring plane becomes obvious on the angle between the Cu– and spectral properties. The hydrogen bond vibrations in the
O3PM bond and the pyridine ring plane (61° for 3 Å, 64° for 2 spectra of all three complexes show broad signals between
and only 32° for [Cu(3,5-(NO2)2bz)2(μ-3PM)2]n). Similar 2530 and 2910 cm–1 which can be attributed to a system of
,
trends could be seen in the D···A–H bond parameters, where intramolecular and/or intermolecular hydrogen bonds (see hy-
A is carboxylate anion oxygen atom {e.g. 2.628(3) Å for 3, drogen bonds formation above). The electronic spectra of the
2.617(2) Å for 2 and 2.753(2) Å for [Cu(3,5-(NO2)2bz)2(μ- three complexes are very similar and exhibit broad asymmetric
3PM)2]n}, which suggest a relation of these geometrical pa- absorption bands attributed to d←d transitions with a maxi-
rameters to the basicity of nitrobenzoato anions (pKa = 3.43 mum positioned at 610 nm for 1, 650 nm for 2, and at 656 nm
for 4-nitrobenzoic [34, 3.46 for 3-nitrobenzoic 34] and 2.79 for 3.
for the 3,5-dinitrobenzoic acid [35]).
The EPR spectra (measured at room temperature) are very
Finally, it should be pointed out that formation of the quasi similar and exhibit axial type with spectroscopic splitting fac-
one-dimensional [Cu(2-NO2bz)2(μ-3PM)2(H2O)2] diaqua com- tors g⊥ = 2.078 and gs = 2.280 for 1, g⊥ = 2.060 and gs = 2.280
plex in comparison to two-dimensional [Cu(2-NO2bz)2(μ- for 2, and g⊥ = 2.080 and gs = 2.285 for 3. It is interesting
3PM)2] could be related to non-planarity because of the bulki- that well resolved parallel hyperfine splitting As = 160 Gauss,
ness of the 2-nitrobenzoate anion, whereas the other three ni- resulting from the interaction of the unpaired electron of the
trobenzoate anions are nearly planar. This deviation from pla- copper atom with the spin of copper nucleus I = 3/2 was ob-
narity could be expressed by the angles φrot (angle between served only for complex 3. It is worth to mention, that this
–CO2 and phenyl ring planes) [36] and φ'rot (the angle be- hyperfine splitting was not observed for complex 2, which is
tween –NO2 and ring planes), which amount 44.0 and 43.7° of very similar molecular structure (Table 1).
for complex 1, and 28.9 and 54.5° for [Cu(2-NO2bz)2(μ-
3PM)2(H2O)2]. In spite of the insertion of water molecules into
Conclusions
both bridges, the hydrogen atom H7 of the pyridine ring forms
C–H···π interaction [37] with 2-nitrobenzoate phenyl [C2–C7]
ring (H7···cg distance 2.9 Å).
Three coordination polymers with copper(II) nitrobenzoate
and the ligand 3-pyridylmethanol were prepared and character-
ized. The crystal structure of 1 consists of 2D sheets. On the
other hand, the crystal structures of 2 and 3 consist of 1D
chains (Table 2), which are linked by face-to-face π–π stacking
interactions. This study has shown that 3-pyridylmethanol is a
suitable bridging ligand for the construction of one- or two-
Preparation and Spectral Properties
The preparations of complexes 1–3 reveal some interesting
features. The best soluble complex 1 was obtained in a smaller
yield under the reaction conditions given in Experimental Sec-
tion and the crystals obtained from mother liquid were not
suitable for X-ray analysis. However, greater dilution (over
50 mL with the same amount of reactants) of reaction mixture
gave clear solution from which the crystals of [Cu(2-
NO2bz)2(3PM)2(H2O)2] were obtained [11]. Moreover, the less
soluble complex 3 was obtained in highest yield and good
crystals were obtained from the light blue mother liquid. All
experiments performed with diluted reaction mixtures yielded
products 2 or 3 in unchanged fashion and we were not able to
obtain a diaqua complex similar to mentioned [Cu(2-
NO2bz)2(3PM)2(H2O)2] [11].
In the IR spectrum of complex 1, the bands corresponding
to νas(COO–) and νs(COO–) are present at 1602 cm–1 and
1371 cm–1, respectively. The value of Δν (Δν = νas–νs) amounts
231 cm–1 and is greater than Δν for the ionic form of the 2-
nitrobenzoate salt (211 cm–1). It corresponds to a monodentate
coordination mode. For complexes 2 and 3, the corresponding
bands are found at 1598 cm–1 and 1376 cm–1 for 2, and at
1578 cm–1 and 1382 cm–1 for 3, respectively. The Δν values
are 222 cm–1 and 196 cm–1, respectively and confirm in both
cases monodentate coordination mode. The monodentate bond-
ing mode of carboxylate anions is typical for complexes with
the 3PM ligand. Nitrobenzoatocopper(II) complexes with other
nitrogen donor ligands (e.g. 2PM, nicotinamide, or diethylnic-
Table 2. Crystal data and structure refinement parameters for com-
plexes 1 and 3.
Compound
1
3
Chemical formula
Mr /g·mol–1
Crystal system
Space group
T /K
C26H22CuN4O10
614.03
orthorhombic
Pbca
C26H22CuN4O10
614.03
triclinic
¯
P1
100(2)
13.031(4)
9.196(3)
21.758(7)
90
293(2)
a /Å
6.878(1)
7.897(1)
12.145(1)
86.65(1)
83.87(1)
78.42(1)
642.08(13)
1
b /Å
c /Å
α /°
β /°
90
90
γ /°
V /Å3
2607.3(14)
4
Z
ρcalcd. /g·cm–3
Radiation type
μ /mm–1
Crystal size /mm
F(000)
1.564
1.588
Mo-Kα
0.918
Cu-Kα
1.773
0.20 × 0.20 × 0.30 0.22 × 0.34 × 0.35
1260
72.45
20465
315
θ
max/°
26.37
Reflections collect.
3265
R1 (2σ)/ wR2 (all data) 0.034/0.096
0.039/0.103
2603/18/202
Data/restrains/
parameters
S
2535/0/188
1.04
0.35/–0.66
1.03
0.30/–0.27
Δρmax./Δρmin. /e·Å–3
592
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 589–594

Coordination Polymers of Copper(II) Nitrobenzoate
[41]. Geometrical analyses were performed using SHELXL-97. The
structures were drawn by XP in SHELXTL [41].
dimensional coordination polymers. Our failed attempt to pre-
pare diaqua complexes with 4-, or 3-nitrobenzoate anions
could be related to a coplanar orientation of the NO2 substitu-
ents and phenyl rings that allow additional structure stabiliza-
tion by π···π stacking interactions of anionic ligands.
The nitro group of complex 3 is orientationally disordered and the
refined site-occupancy factors of the three disordered parts are 0.66,
0.11 and 0.23, respectively. The N–O, O···O and C···O distances were
restrained by SADI instructions of SHELXL-97. Thermal ellipsoids
of disordered nitro-groups were constrained by EADP instructions of
SHELXL-97.
Experimental Section
Physical Measurements
Crystallographic data for the structural analysis were deposited with
the Cambridge Crystallographic Data Centre CCDC-741830 (1), and
-741831 (3). Further details of the crystal structures investigations are
available free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; +44-
1223-336033; E-Mail: deposit@ccdc.cam.ac.uk).
Carbon, hydrogen and nitrogen analyses were carried out with a
CHNSO FlashEATM 1112 automatic elemental analyzer. The copper
content was determined by electrolysis of water solution obtained by
the sample mineralization with a mixture of sulfuric acid and potas-
sium peroxodisulfate.
The electronic spectra (190–1100 nm) of the complexes were meas-
ured in nujol suspension with a SPECORD 200 (Carl Zeiss Jena) spec-
trophotometer at room temperature. The infrared spectra (4000–
100 cm–1) were recorded with a MAGNA 750 IR (Nicolet) and Nicolet
5700 FT-IR spectrophotometers at room temperature. EPR spectra of
Supporting Information (see footnote on the first page of this article):
The supplementary figures S1–S3.
Acknowledgement
the powdered samples were recorded with
Bruker ER 200-SRC operating at X-band.
a
spectrometer
We thank the Scientific Grant Agency of the Ministry of Education of
the Slovak Republic and the Slovak Academy of Sciences for financial
support (1/4454/07) and the Research and Development Agency of the
Slovak Republic (No. APVT-20-004504).
Preparation of the Complexes
The blue complexes were prepared by similar reactions of aqueous
solutions of copper(II) acetate (1 mmol in 10 mL) with 3-pyridylmeth-
anol (ronicol, 2 mmol). 2-Nitrobenzoic acid (2 mmol for 1), 3-nitrob-
enzoic (2 mmol for 2) or 4-nitrobenzoic acid (2 mmnol for 3) was
added with water (10 mL), and the reaction mixtures were stirred until
blue powders formed. The products were filtered off (0.10 mmol of 1,
0.28 mmol of 2 and 0.57 mmol of 3), washed with a small amount of
cold water and dried at room temperature. Blue crystals suitable for
X-ray analysis of 2 and 3 were obtained from the aqueous mother
liquids after one week at room temperature. The crystals obtained for
1 were not good enough for X-ray analysis, suitable single crystals
were obtained by the same procedure using ethanol instead of water
as solvent (0.80 mmol of 1).
References
[1] a) C. Janiak, Dalton Trans. 2003, 2781–2804; b) C. N. R. Rao, S.
Natarajan, R. Vaidhyanathan, Angew. Chem. Int. Ed. 2004, 43,
1466–1496; c) S. L. James, Chem. Soc. Rev. 2003, 32, 276–288.
[2] a) S. Taheri, F. Marandi, H.-K. Fun, R. Kia, Z. Anorg. Allg. Chem.
2009, 635, 1352–1354; b) S. K. Henninger, H. A. Habib, C. Jan-
iak, J. Am. Chem. Soc. 2009, 131, 2776–2777; c) H. A. Habib, J.
Sanchiz, C. Janiak, Dalton Trans. 2008, 4877–4884; d) J. L. Xiel,
Z. Anorg. Allg. Chem. 2009, 635, 384–388; e) I. Stein, U. Rusche-
witz, Z. Anorg. Allg. Chem. 2009, 635, 914–919; f) M. Bröring,
S. Prikhodovski, Z. Anorg. Allg. Chem. 2008, 634, 2451–2458;
g) F. Marandi, M. Khosravi, H. K. Fun, Z. Anorg. Allg. Chem.
2008, 634, 2617–2628; h) A. Kromm, Y. Geldmacher, W. S. Shel-
drick, Z. Anorg. Allg. Chem. 2008, 634, 2191–2198; i) K. Müller-
Buschbaum, Y. Mokaddem, Z. Anorg. Allg. Chem. 2008, 634,
2360–2366; j) R. Koferstein, C. Robl, Z. Anorg. Allg. Chem.
2007, 633, 1127–1130; k) J.-P. Zou, G.-S. Zeng, Z.-H. Wen, Q.
Peng, Q.-J. Xing, M.-H. Chen, G.-C. Guo, J.-S. Huang, Inorg.
Chim. Acta 2009, 362, 4843–4848; l) M. Wriedt, C. Nather, Z.
Anorg. Allg. Chem. 2009, 635, 1115–1122; m) W.-W. Sun, X.-B.
Qian, C.-Y. Tian, E.-Q. Gao, Inorg. Chim. Acta 2009, 362, 2744–
2748; n) D. P. Martin, R. M. Supkowski, R. L. LaDuca, Cryst.
Growth Des. 2008, 8, 3518–3520; o) B. Xiao, P. J. Byrne, P. S.
Wheatley, D. S. Wragg, X.-B. Zhao, A. J. Fletcher, K. M.
Thomas, L. Peters, J. S. O. Evans, J. E. Warren, W. Z. Zhou,
R. E. Morris, Nat. Chem. 2009, 1, 289–294.
[Cu(2-NO2bz)2(μ-3PM)2]n (1): calcd. C 50.86, H 3.61, N 9.13, Cu
10.35; found C 50.92, H 3.60, N 9.17, Cu 10.44.
[Cu(3-NO2bz)2(μ-3PM)2]n (2): calcd. C 50.86, H 3.61, N 9.13 Cu
10.35; found C 50.97 H 3.65 N 9.14 Cu 10.35.
[Cu(4-NO2bz)2(μ-3PM)2]n (3): calcd. C 50.86, H 3.61, N 9.13, Cu
10.35; found C 50.86, H 3.82, N 8.79, Cu 10.00 %.
X-ray Crystallography
The crystal data and details of data collections for all structures are
given in Table 2. Intensity data for 1 were collected with a Xcalibur [3] J.-R. Li, R. J. Kuppler, H.-C. Zhou, Chem. Soc. Rev. 2009, 38,
1477–1504.
PX κ-diffractometer [38] with graphite-monochromated Cu-Kα radia-
tion and CCD detector at 100 K. Data for 3 were collected with a
diffractometer Siemens P4 [39] with graphite-monochromated Mo-Kα
radiation at 293 K. The diffraction intensities were corrected for Lo-
rentz and polarization effects. Absorption corrections were applied us-
ing the programs CrysAlis-RED [38] for 1 and XEMP [39] for 3. The
structures were solved by direct methods using the programs SIR-97
[40] (for 1) or SHELXS-97 [41] (for 3) and refined by the full-matrix
least-squares method on all F2 data using the program SHELXL-97
[4] J.-Y. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nquyen,
J. T. Hupp, Chem. Soc. Rev. 2009, 38, 1450–1459.
[5] O. R. Evans, W. B. Lin, Acc. Chem. Res. 2002, 35, 511–522.
[6] M. D. Allendorf, C. A. Bauer, R. K. Bhakta, R. J. T. Houk,
Chem. Soc. Rev. 2009, 38, 1330–1352.
[7] S. Kitagawa, K. Uemura, Chem. Soc. Rev. 2005, 34, 109–119.
[8] D. Maspoch, D. Ruiz-Molina, J. Veciana, J. Mater. Chem. 2004,
14, 2713–2723; M. Kurmoo, Chem. Soc. Rev. 2009, 38, 1353–
1379.
Z. Anorg. Allg. Chem. 2010, 589–594
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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J. Moncol et al.
ARTICLE
[9] a) J. E. Beves, E. C. Constable, C. E. Housecroff, M. Neuburger, [21] V. Zelenak, I. Cisarova, M. Sabo, P. Llewellyn, K. Gyoryova, J.
S. Schaffner, Inorg. Chem. Commun. 2009, 12, 898–901; b) M. G.
Amiri, A. Morsali, M. Zeller, Z. Anorg. Allg. Chem. 2009, 635,
1673–1677; c) N. Lah, R. Clerac, Polyhedron 2009, 28, 2466–
2472; d) H. A. Habib, J. Sanchiz, C. Janiak, Inorg. Chim. Acta
2009, 362, 2452–2460; e) M. C. Das, P. K. Bharadwaj, J. Am.
Chem. Soc. 2009, 131, 10942–10949; f) H. A. Habib, A. Hoff-
mann, H. A. Höppe, G. Steinfeld, C. Janiak, Inorg. Chem. 2009,
48, 2166–2180; g) H. A. Habib, A. Hoffmann, H. A. Höppe, C.
Janiak, Dalton Trans. 2009, 1742–1751; h) J. Yang, J.-F. Ma, Y.-
Y. Liu, S. R. Batten, CrystEngComm 2009, 11, 151–159; i) H. A.
Habib, J. Sanchiz, C. Janiak, Dalton Trans. 2008, 1734–1744;
j) M. Du, Z.-H. Zhang, X.-G. Wang, L.-F. Tang, X.-J. Zhao, Crys-
tEngComm 2008, 10, 1855–1865; k) P. P. Yang, B. Li, Y. H.
Wang, W. Gu, X. Liu, Z. Anorg. Allg. Chem. 2008, 634, 1210–
1214; l) Y.-Q. Lan, S.-L. Li, Y.-M. Fu, Y.-H. Xu, L. Li, Z.-M. Su,
Q. Fu, Dalton Trans. 2008, 6796–6807; m) W. Yu, T. L. Zhang,
J. G. Zhan, L. Yang, S. Z. Wang, R. F. Wu, Z. Anorg. Allg. Chem.
2008, 634, 754–757; n) Q. Y. Wen, J. Q. Chen, H. C. Fang, L.
Chen, Z. Y. Zhou, Z. J. Hu, Y. P. Cai, Z. Anorg. Allg. Chem. 2008,
634, 567–571; o) C. Y. Sun, X. X. Li, S. F.Wang, W. J. Li, X. J.
Zheng, Z. Anorg. Allg. Chem. 2008, 634, 950–955; p) P. Ren, M.-
L. Liu, J. Zhang, W. Shi, P. Cheng, D.-Z. Liao, S.-P. Yan, Dalton
Trans. 2008, 4711–4713.
Coord. Chem. 2004, 57, 87–96.
[22] J. Moncol, D. Miklos, P. Segla, M. Koman, T. Lis, Acta Crystal-
logr., Sect. E 2008, 64, m440–m441.
[23] M. Melnik, K. Smolander, P. Sharrock, Inorg. Chim. Acta 1985,
103, 187–194.
[24] J. Moncol, P. Segla, J. Jaskova, A. Fischer, M. Melnik, Acta Crys-
tallogr., Sect. E 2007, 63, m698–m700.
[25] J. Moncol, M. Mudra, P. Lönnecke, M. Koman, M. Melnik, J.
Chem. Crystallogr. 2004, 34, 423–431.
[26] J. Jaskova, D. Miklos, P. Segla, R. Sillanpää, J. Moncol, Acta
Crystallogr., Sect. E 2007, 63, m910–m912.
[27] S. Stefanikova, I. Ondrejkovicova, M. Koman, T. Lis, J. Mrozin-
ski, M. Wrzecion, J. Coord. Chem. 2008, 61, 3895–3903.
[28] M. A. S. Goher, F. A. Mautner, K. Gatter, M. A. M. Abu-Yous-
sef, A. M. A. Badr, B. Sodin, C. Gspan, J. Mol. Struct. 2008,
876, 199–205.
[29] R. P. Feazell, C. E. Carson, K. K. Klausmeyer, Inorg. Chem.
Commun. 2007, 10, 873–875.
[30] F. J. Ramos-Lima, O. Vrana, A. G. Quiroga, C. Navarro-Ran-
ninger, A. Halamikova, H. Rybnickova, L. Hejmalova, V. Brabec,
J. Med. Chem. 2006, 49, 2640–2651.
[31] A. Martinez, J. Lorenzo, M. J. Prieto, M. Font-Bardia, X. Solans,
F. X. Aviles, V. Moreno, Bioorg. Med. Chem. 2007, 15, 969–979.
[32] J. Moncol, J. Maroszova, M. Melnik, M. Koman, Acta Crystal-
logr., Sect. C 2007, 63, m114–m116.
[33] C. Janiak, Chem. Soc., Dalton Trans. 2000, 3885–3896.
[34] P. D. Bolton, K. A. Fleming, F. M. Hall, J. Am. Chem. Soc. 1972,
94, 1033–1034.
[10] J. Moncol, P. Segla, D. Miklos, M. Mazur, M. Melnik, T. Głow-
iak, M. Valko, M. Koman, Polyhedron 2006, 25, 1561–1566.
[11] P. Stachová, M. Korabik, M. Koman, M. Melník, J. Mrozinski, T.
Głowiak, M. Mazúr, D. Valigura, Inorg. Chim. Acta 2006, 359,
1275–1281.
[12] M. Mudra, J. Moncol, J. Svorec, M. Melnik, P. Lönnecke, T.
Głowiak, R. Kirmse, Inorg. Chem. Commun. 2003, 6, 1259–1265.
[13] P. Stachova, D. Valigura, M. Koman, T. Głowiak, Acta Crystal-
logr., Sect. E 2005, 61, m994mm996.
[35] S. L. Gupta, R. N. Soni, J. Indian Chem. Soc. 1965, 42, 377–378.
[36] T. Kawata, H. Uekusa, S. Ohba, T. Furukawa, T. Tokii, Y. Muto,
M. Kato, Acta Crystallogr., Sect. B 1992, 48, 253–261.
[37] H. Suezawa, T. Yoshida, Y. Umezawa, S. Tsuboyama, M. Nishio,
Eur. J. Inorg. Chem. 2002, 3148–3155.
[14] F. Valach, M. Tokarcik, P. Kubinec, M. Melnik, L. Macaskova,
Polyhedron 1997, 16, 1461–1464.
[15] V. Jorík, E. Scholtzová, P. Segla, Z. Kristallogr. 2008, 223, 524–
529.
[38] Oxford Diffaraction, CrysAlis CCD and CrysAlis RED, Oxford
Diffraction Ltd, Abingdon, England, 2006.
[16] J. Maroszova, L. Martiska, D. Valigura, M. Koman, T. Głowiak,
Acta Crystallogr., Sect. E 2006, 62, m1164–m1166.
[39] Siemens, XSCANS and XEMP, Siemens Analytical X-ray Instru-
ments Inc., Madison, Wisconsin, USA, 1994.
[17] S. Lörinc, M. Koman, M. Melnik, J. Moncol, D. Ondrusova, Acta
Crystallogr., Sect. E 2004, 60, m590–0592.
[40] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Gia-
covazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spa-
gna, J. Appl. Crystallogr. 1999, 32, 115–119.
[18] N. N. Hoang, F. Valach, L. Macaskova, M. Melnik, Acta Crystal-
logr., Sect. C 1992, 48, 1933–1936.
[41] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
[19] J. Maroszova, J. Moncol, M. Koman, M. Melnik, T. Głowiak,
Acta Crystallogr., Sect. E 2006, 62, m3385–m3387.
Received: June 26, 2009
[20] J. Moncol, M. Koman, M. Melnik, T. Głowiak, CrystEngComm
2001, 3, 262–264.
Published Online: December 9, 2009
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Z. Anorg. Allg. Chem. 2010, 589–594