Synthesis, crystal structures and properties of [Cu(L1)2(Py) 2(H2O)](H2O) [HL1 = N-(5-ethyl-[1,3,4]- thiadiazole-2-yl)-toluenesulfonamidate] and [Cu(L2)2(py) 2(H2O)] [HL2 = N-(5-ethyl-[1,3,4]-thiadiazole-2-yl) benzenesulfonamidate]

Article abstract of DOI:10.1002/zaac.200700214

A series of new N-sulfonamidate ligands and their cooperai) complexes, [Cu(N-(5-ethyl-[ 1,3,4]-thiadiazole-2-yl)-toluenesulfonamidate) ₂(py)₂(H₂O)](H₂O) (1) and [Cu(N-(5-ethyl-[1,3,4]thiadiazole-2-yl)-benzenesulfonamidate) ₂(py)₂(H₂O)] (2) have been synthesized and characterized. The X-ray crystal structures of the complexes 1 and 2 have been determined. In the both two complexes, the Cu²⁺ ion is five-coordinated, forming a CuN₄O chromophore. The ligands act as monodentate, coordinating the metal ion through a single N^thiadiazole atom. The molecules from the reaction medium (pyridine and water) also participate to the coordination of Cu²⁺ ion as monodentate ligands. Both two complexes have a slightly distorted square pyramidal geometry. The chemical properties of the complexes have been studied by FT-IR, electronic and EPR spectroscopic methods.

Full text of DOI:10.1002/zaac.200700214

DOI: 10.1002/zaac.200700214
Synthesis, Crystal Structures and Properties of [Cu(L1)2(py)2(H2O)](H2O)
[HL1 ؍ N-(5-ethyl-[1,3,4]؊thiadiazole-2-yl)-toluenesulfonamidate] and
[Cu(L2)2(py)2(H2O)] [HL2 ؍ N-(5-ethyl-[1,3,4]؊thiadiazole-2-yl)-
benzenesulfonamidate]
Adriana Hangana, Joaquin Borrasb,*, Malva Liu-Gonzalezc, and Luminita Opreana
¸
a Cluj-Napoca/Romania, Universitatea de Medicina si Farmacie, Facultatea deFarmacie, Catedra de Chimie Generala si Anorganica
Burjassot/Spain, Universidad de Valencia, b Departamento de Quimica Inorganica, Facultad de Farmacia and c Departamento de
Termologia
Received May 2nd, 2007.
Dedicated to Professor Alfonso Castineiras on the Occasion of his 65th Birthday
Abstract. A series of new N-sulfonamidate ligands and their coop-
er(II) complexes, [Cu(N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-toluene-
sulfonamidate)2(py)2(H2O)](H2O) (1) and [Cu(N-(5-ethyl-[1,3,4]-
thiadiazole-2-yl)-benzenesulfonamidate)2(py)2(H2O)] (2) have been
synthesized and characterized. The X-ray crystal structures of the
complexes 1 and 2 have been determined. In the both two com-
plexes, the Cu2ϩ ion is five-coordinated, forming a CuN4O chromo-
phore. The ligands act as monodentate, coordinating the metal ion
through a single Nthiadiazole atom. The molecules from the reaction
medium (pyridine and water) also participate to the coordination
of Cu2ϩ ion as monodentate ligands. Both two complexes have a
slightly distorted square pyramidal geometry. The chemical proper-
ties of the complexes have been studied by FT-IR, electronic and
EPR spectroscopic methods.
Keywords: Copper; Sulfonamides; Crystal structures
Introduction
cyclic sulfonamides: HL1
zoleϪ2-yl)-toluenesulfonamide and HL2
ϭ
N-(5-ethyl-[1,3,4]Ϫthiadia-
N-(5-ethyl-
ϭ
The study of N-substituted heterocyclic sulfonamide ligands
was shown their ability to coordinate biologically important
metallic ions. The sulfonamides structures are varied and
complex, and offer multiple possibilities to coordinate met-
allic ions depending on the type of donors atoms in the
molecule (O, S, N), the stereochemistry of the compounds,
the nature of the metallic ion that can form complexes, the
nature of the anion of the salt that offers the central ion,
the conditions for the synthesis of the complexes [1Ϫ4].
The pharmacological activity and the chelating proper-
ties of sulfonamides allow the synthesis of metallic com-
plexes with various therapeutic activities, which serve as
models for metalloenzymes [5Ϫ11].
[1,3,4]ϪthiadiazoleϪ2-yl)-benzenesulfonamide (scheme 1).
Two complexes of these sulfonamido ligands with Cu2ϩ were
prepared and their structures determined by X-ray diffraction.
Their IR, ESR, electronic spectra and its magnetic suscepti-
bility were investigated and discussed, along with the struc-
tural and spectral comparisons with those of the analogous
complexes.
Metallic ions, including Cu2ϩ, and their coordinative
compounds, can produce in the presence of reducing agents,
reactive free radical species which can cleavage the DNA
molecule. This property has spurred studies concerning
their use in complexes with Fe2ϩ, Mn2ϩ, Cu2ϩ etc. ions as
potential “artificial chemical nucleases” [3, 4, 10, 11].
In the present paper we report the synthesis and the physico-
chemical characterization of two news N-substituted hetero-
Scheme 1
Results and Discussion
´
* Prof. Dr. J. Borras
Crystal structures of [Cu (L1)2(py)2(H2O)](H2O) (1)
and [Cu (L2)2(py)2(H2O)] (2)
Departamento de Quimica Inorganica. Facultad de Farmacia
Avda. Vicent Andres Estelles s/n
46100-Burjassot, Spain
Relevant bond distances and angles for the complexes 1 and 2
Fax: -34 963544960
E-mail: Joaquin.Borras@uv.es
are collected in Table 1.
Z. Anorg. Allg. Chem. 2007, 633, 1837Ϫ1841
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1837

A. Hangan, J. Borras, M. Liu-Gonzalez, L. Oprean
˚
thiadiazole rings Nthiadiazole from the sulfonamidate ligands
Table 1 Selected bond distances /A and angles /° for compounds
1 and 2
and two nitrogen atoms from each pyridine molecules Npyridine
The CuϪNthiadiazole lengths (1.986 (4)Ϫ2.004 (4) A) are
smaller than those corresponding to the other complexes with
.
˚
1
2
ligands containing a thiadiazole ring [12, 13]. CuϪNpyridine
lengths (2.055 (4)Ϫ2.062 (5) A) are consonant with those
measured for similar compounds. One water O atom [O(1W)
Bond distances
Cu(1)ϪN(2a)
Cu(1)ϪN(2b)
Cu(1)ϪN(2)
Cu(1)ϪN(1)
Cu(1)ϪO(1W)
Bond distances
Cu(1)ϪN(2b)
Cu(1)ϪN(2a)
Cu(1)ϪN(1)
Cu(1)ϪN(2)
Cu(1)ϪO(1W)
˚
1.986(4)
2.004(4)
2.055(4)
2.062(5)
2.216(4)
1.987(3)
1.987(3)
2.059(3)
2.059(3)
2.232(4)
in 1 and 2] occupies the axial position with a bond length of
˚
˚
2.216(4) A (1) and 2.232(4) A (2). The angles between the
atoms in the equatorial plane are of about 90°
[87.3(2)Ϫ90.7(2)° (1) and 88.44(12)Ϫ90.97(12)° (2)] and those
between the atoms on the axial plane and the equatorial plane
are similar [93.3(2)Ϫ97.9(2)° (1) and 92.65 (9)Ϫ96.44 (10)°
(2)]. The distances almost equal between Cu and N atoms in
the ecuatorial plane, the distance significantly bigger between
Cu and O atom in the axial plane and the angles forming the
coordination polyhedron confirm the slightly distorted square
pyramidal structure for the complexes 1 and 2. The bond-
length change are described by the tetragonality (T5). The tet-
ragonality values, 0.91 (compound 1) and 0.91 (compound 2),
fit into the range expected for square pyramidal complexes
[14]. The in-plane angular distortions described by the ratio
τ represents a percentage of trigonal distortion of a square-
pyramidal geometry [15]. The τ value of 0.08 for compound 1
and 0.12 for compound 2 indicates a very slight distortion. It
is noteworthy that the coordination of Cu2ϩ takes place
through the Nthiadiazole atom instead though the deprotonated
Bond angles
N(2a)ϪCu(1)ϪN(2b) 165.7(2)
Bond angles
N(2b)ϪCu(1)ϪN(2a) 174.7(2)
N(2a)ϪCu(1)ϪN(2)
N(2b)ϪCu(1)ϪN(2)
N(2a)ϪCu(1)ϪN(1)
N(2b)ϪCu(1)ϪN(1)
N(2)ϪCu(1)ϪN(1)
N(2a)ϪCu(1)ϪO(1W) 97.9(2)
N(2b)ϪCu(1)ϪO(1W) 96.3(2)
89.4(2)
90.7(2)
90.3(2)
87.3(2)
170.5(2)
N(2b)ϪCu(1)ϪN(1)
N(2a)ϪCu(1)ϪN(1)
N(2b)ϪCu(1)ϪN(2)
N(2a)ϪCu(1)ϪN(2)
N(1)ϪCu(1)ϪN(2)
N(2b)ϪCu(1)ϪO(1W) 92.65(9)
N(2a)ϪCu(1)ϪO(1W) 92.65(9)
88.44(12)
90.97(12)
90.97(12)
88.44(12)
167.10(2)
N(2)ϪCu(1)ϪO(1W)
N(1)ϪCu(1)ϪO(1W)
96.2(2)
93.3(2)
N(1)ϪCu(1)ϪO(1W)
N(2)ϪCu(1)ϪO(1W)
96.44(10)
96.44(10)
Figures 1 and 2 show molecular structures with the atom
numbering scheme of the complexes 1 and 2, respectively.
Nsulfonamido atom. This is a consequence of the charge delocal-
ization between the sulfonamido and the thiadiazole ring. In
the complexes 1 and 2, the both sulfonamidate ligands (HL1)
and (HL2) acting as monodentate as they coordinate through
a nitrogen atom of the thiazole heterocycle. The sulfonamide
molecules of this type can behave as bidentate ligands as well
through the N atom from the thiadiazole moiety and through
one of the O atoms and even through the Nsulfonamido atom
from the sulfonamido moiety [16]. As it is expected the pyri-
dine and the water molecules participate in the coordination as
monodentate ligands. For the complex 1, the crystalline pack-
ing of the symmetrical unit also includes a water molecule
from the reaction medium, that does not coordinate the Cu2ϩ
ion.
Fig. 1 ORTEP drawing of the [Cu(L1)2(py)2(H2O)](H2O) (1)
complex
Spectroscopic and magnetic properties
The IR spectra of both complexes present a similar pattern.
The most remarkable difference occurs in the band corre-
sponding to the stretching vibration of the thiadiazole ring,
which is shifted from 1530 cmϪ1 (HL1) and 1565 cmϪ1 (HL2)
in the free ligands to 1444 cmϪ1 (1) and 1510 cmϪ1 (2) in the
complexes. The characteristic band corresponding to the
ν(SϪN) appears at 932 cmϪ1 (1) and 935 cmϪ1 (2) shifted ca.
20 cmϪ1 to higher frequencies with respect to those of the un-
coordinated ligands. These modifications in the thiadiazole
heterocycle and in the sulfonamide group are attributed to the
involvement to the Nthiadiazole atom in coodination of Cu2ϩ
and to the deprotonation of the sulfonamido moiety [17Ϫ19].
Fig. 2 ORTEP drawing of the [Cu(L2)2(py)2(H2O)] (2) complex
The crystal structures of 1 and 2 contain a CuN4O entity
in a slightly distorted square pyramidal geometry. In the basal
plane Cu2ϩ is coordinated by two nitrogen atoms of the two
1838
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 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1837Ϫ1841

[Cu(L1)2(py)2(H2O)](H2O) and [Cu(L2)2(py)2(H2O)]
Bands due to the antisymmetric and symmetric vibration
modes of the SϭO2 bonds are recorded close to 1319 and
1142 cmϪ1, ca. 20 cmϪ1 lower than those corresponding to the
free ligands [20, 21]; such a decrease can be related to the elec-
tron transfer from the deprotonated, negatively charged N
atom to the sulfonyl oxygen atoms, which results in partial
single-bond character for the SϪO bonds [22]. Such electron
transfer increases the bond order of the SϪN moiety, thus ac-
counting for the 25 cmϪ1 shift towards higher wavenumbers of
the band due to the stretching mode of this bond. The lack of
bands close to 3200 cmϪ1, which were originally present in the
spectra of the free ligands confirm deprotonation of the NϪH
bonds. This deprotonation of Nsulfonamido atom determines a
weak conjugation effect among the three N, S, O atoms of the
moiety. Literature indicates that the bands corresponding to
the coordinated pyridine molecules participating in the coordi-
to the Bertini classification, the value of Aʈ for complex 1 can
be correlated with the structure of the complex [28]. Thus, val-
ues between 130 and 160 cmϪ1 correspond to a square pyrami-
dal or distorted trigonal bipyramidal arrangement. As gʈ > g֊
2
2
in the complexes, the unpaired electron must be in the dx Ϫy
(or dxy) orbital [23]. The EPR parameters of complex 1 and 2
reflect the square pyramidal coordination of Cu2ϩ ion.
The room temperature magnetic moments of complexes 1
(µeff ϭ 1.73 MB) and 2 (µeff ϭ 1.83 MB) are consistent with the
presence of a single unpaired electron.
Experimental Section
Materials and physical measurements
nation appear at 3057 cmϪ1
, , ,
1450 cmϪ1 1080 cmϪ1
Copper sulfate pentahydrate, benzenesulfonylchloride, toluenesulfon-
ylchloride, 2-amino-5-ethyl-[1,3,4]Ϫthiadiazole and pyridine were
purchased from commercial sources and used as received.
1035 cmϪ1, 1008-995 cmϪ1, 660 cmϪ1, 440 cmϪ1 [23Ϫ25]. In
the IR spectrum of the both complexes a band appears at ca.
1085 cmϪ1, interpreted as corresponding to pyridine (as it
does not appear in the free ligands spectrum). The other bands
be attributed to pyridine, as they sometimes overlap the fre-
quencies corresponding to moieties of the ligand. In general,
the patterns of the IR spectra are similar to those observed for
other cooper N-sulfonamide derivatives [4, 21].
The solid electronic spectra of the both complexes display a
band near 400 nm (396 nm for complex 1 and 401 nm for com-
plex 2) assigned to a LMCT transition. The complex 1 exhibits
a d-d band at 591 nm and the complex 2 show a d-d band at
583 nm. This pattern, characteristic for distorted square-pyr-
amidal cooper(II) complexes, agrees well with the crystallo-
graphic data [26].
Elemental analysis(C, N, H, S) were performed on a Perkin-Elmer de-
vice, using the combustion technique. IR spectra were recorded with a
Perkin-Elmer FT-IR 1730 spectrophotometer using powder samples
in KBr disks, in the 4000-400 cmϪ1 range. Fast ion bombardment
(FAB) mass spectra were obtained on a VG Autospec spectrometer in
m-nitrobenzene as a solvent. Diffuse reflectance spectra (nujol mulls)
were carried out on a Shimadzu UV-2101 PC spectrophotometer.
Magnetic susceptibilities were measured at room temperature with the
Faraday MSB-MKI balance. Hg[Co(NCS)4] was used as susceptibility
standard. Electronic paramagnetic resonance (EPR) spectra were per-
formed at room temperature with a Bruker ELEXSYS spectrometer
operating at the X-band frequency.
The polycrystalline X-band EPR spectra of both complexes
are axial. The EPR parameters, obtained by simulation [27] are
gʈ ϭ 2.22, g֊ ϭ 2.069 and Aʈ ϭ 150 x 10Ϫ4 cmϪ1 for complex
1 (figure 3) and gʈ ϭ 2.23, g֊ ϭ 2.05 for complex 2. According
Syntheses of the ligands
N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-
toluenesulfonamide (HL1)
A solution containing 1 mmol of 2-amino-5-ethyl-[1,3,4]-thiadiazole
and 0.9 mmoles of toluenesulfonylchloride in 6 ml of pyridine was
heated at reflux for 1 h, at 60 °C. The mixture was added to 10 ml of
cold water and stirred for several minutes. The resulting solid was
recrystallized from ethanol. Data for HL1(yield 87 %). C11H13N3S2O2
(283): C 46.64 (calc.46.70); H 4.59 (4.63); N 14.84 (14.80); S 22.61
(22.65) %.
IR (KBr) (νmax (cmϪ1)): 1530 (thiadiazole); 1319, 1142 ν(SO2); 916 ν(SϪN).
Solid UV/Vis (λmax) (nm): 318 (πǞπ*). FAB: m/z 284 [MϪHϩ].
N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-
benzenesulfonamide (HL2)
This ligand was obtained following the procedure described above. In
this case, 1 mmol of 2-amino-5-ethyl-[1,3,4]-thiadiazole and
0.9 mmoles of benzenesulfonylchloride were mixed. Data for HL2
(yield 72 %). C10H11N3S2O2 (269): C 44.65 (calc. 44.60); H 4.06 (4.08);
N 15.54 (15.61); S 23.80 (23.79) %.
IR (KBr) (νmax /cmϪ1)): 1565 (thiadiazole); 1315, 1154 ν(SO2); 918 ν(SϪN).
Solid UV/Vis (λmax) (nm): 312 (πǞπ*). FAB: m/z 270 [MϪHϩ].
Fig. 3 X Band EPR of the compound 1
Z. Anorg. Allg. Chem. 2007, 1837Ϫ1841
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1839

A. Hangan, J. Borras, M. Liu-Gonzalez, L. Oprean
were performed with the programs HKL Denzo and Scalepack [30].
Unit cell dimensions were determined from 8270 reflections between
θ ϭ 0.998° and 27.485°. Crystal structure was solved by direct meth-
ods, using the program SIR-97 [31]. Anisotropic least-squares refine-
ment was carried out with SHELXL-97 [32]. All non hydrogen atoms
were anisotropically refined. Hydrogen atoms were located in a differ-
ence Fourier map and located geometrically. Geometrical calculations
were made with PARST [33, 34]. The crystallographic plots were made
with ORTEP [35]. A summary of the crystal data, experimental details
and refinement results is listed in Table 2.
Synthesis of the complexes
[Cu(N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-
toluenesulfonamidate)2(py)2(H2O)](H2O) (1) and
[Cu(N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-
benzenesulfonamidate)2(py)2(H2O)] (2)
A solution of CuSO4· 5H2O (4 mmol) in 20 ml of pyridine : H2O
[v : v ϭ 1 : 1] was added dropwise, under continuous stirring to a solu-
tion of HL1 respectively HL2 ligand (1 mmol) dissolved in 25 ml pyri-
dine : H2O [v : v ϭ 2 : 3]. The resulting solution was stirred at room
temperature for one hour and left to stand at room temperature. After
one respectively three months by the slow evaporation of the solvent,
blue crystals (compound 1) and green-blue crystals (compound 2) suit-
able for X-ray diffraction were obtained.
Data collection of [Cu (L2)2(py)2(H2O)] (2). A blue crystal, size 0.12 ϫ
0.14 ϫ 0.16 mm, monoclinic, space group P2/n (determined from the
systematic absences) was used. Data collection was performed at
293° K on a Nonius Kappa-CCD single crystal diffractometer, using
Data for compound 1: (yield 65 %). C32H38CuN8S4O6 (822.4): C 46.68
(calc. 46.71); H 4.64 (4.62); N 13.64 (13.62); S 15.68 (15.57) %.
˚
Mo Kα radiation (λ ϭ 0.7173 A). Crystal-detector distance was fixed
at 40 mm, and a total of 162 images were collected using the oscillation
method, with scan angle per frame 2° oscillation and 10s exposure time
per image. Data collection strategy was calculated with the program
Collect [29]. Data reduction and cell refinement were performed with
the programs HKL Denzo and Scalepack [30]. Crystal structure was
solved by direct methods, using the program SIR-97 [31]. Anisotropic
Least-squares refinement was carried out with SHELXL-97 [32]. All
non hydrogen atoms were anisotropically refined. Hydrogen atoms
were located in a difference Fourier map and located geometrically.
Geometrical calculations were made with PARST [33, 34]. The crystal-
lographic plots were made with ORTEP [35]. A summary of the crystal
data, experimental details and refinement results is listed in Table 2.
IR (KBr) (νmax /cmϪ1)): 1444 (thiadiazole); 1300, 1142 ν(SO2); 932 ν(SϪN).
Solid UV/Vis (λmax) (nm): 300 (πǞπ*), 396 (LMCT), 591 (d-d).
Data for compound 2: (yield: 58 %). C30H32CuN8S4O5 (776.42): C
46.39 (calc. 46.43); H 4.12 (4.10); N 14.43 (14.38); S 16.49 (16.49) %.
IR (KBr) (νmax (cmϪ1)): 1510 (thiadiazole); 1298, 1136 ν(SO2); 935 ν(SϪN).
Solid UV/Vis (λmax) (nm): 314 (πǞπ*), 401(LMCT), 583 (d-d).
X-ray structure determination
Data collection of [Cu (L1)2(py)2(H2O)](H2O) (1). A blue crystal, size
0.15 ϫ 0.19 ϫ 0.25 mm, monoclinic, space group P21/c (determined
from the systematic absences) was used. Data collection was per-
formed at 293° K on a Nonius Kappa-CCD single crystal dif-
Crystallographic data without structure factors fot the two strctures
reported in this paper have been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publications no. CCDC
645240 and CCDC 645241. Copies of the data can be obtained free of
change from the CDCC, 12 Union Road, Cambridge CB2 1EZ, UK:
e-mail for deposition:deposit@ccdc.cam.ac.uk, fax: ϩ44-1223-
336033.
˚
fractometer, using Mo Kα radiation (λ ϭ 0.7173 A). Crystal-detector
distance was fixed at 35 mm, and a total of 90 images were collected
using the oscillation method, with scan angle per frame 2° oscillation
and 12s. exposure time per image. Data collection strategy was calcu-
lated with the program Collect [29]. Data reduction and cell refinement
Table 2 Crystal data and refinement for [Cu(L1)2(py)2(H2O)](H2O) (1) and [Cu(L2)2(py)2(H2O)] (2)
Complexes
1
2
Empirical formula
Formula weight
Temperature
C32 H38 Cu N8 O6 S4
822.4
C30 H32 Cu N8 O5 S4
776.42
293(2) K
293(2) K
˚
˚
Wavelength
0.71073 A
0.71073 A
Crystal system, space group
Unit cell dimensions
monoclinic, P21/c
monoclinic, P/n2
a ϭ 13.9020(4) A
˚
˚
a ϭ 15.9070(4) A
˚
˚
b ϭ 15.6950(4) A β ϭ 118.3131(10)°
b ϭ 9.1690(2) A β ϭ 107.6010(12)°
˚
˚
c ϭ 17.4540(5) A
c ϭ 14.4230(4) A
Volume
3836.27(18) A3
1752.40(8) A3
Z
4
4
Calculated density
Absorption coefficient
F(000)
1.424 Mg/m3
1.471 Mg/m3
0.840 mmϪ1
1708
0.912 mmϪ1
802
Crystal size
θ range for data collection
Limiting indices
Reflections collected/unique
Completeness to θ ϭ 27.48
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I>2σ(I)]
R indices (all data)
Largest diff. Peak and hole
0.15 ϫ 0.19 ϫ 0.25 mm
1.93 to 27.48°
Ϫ20Յ h Յ20, Ϫ18Յ k Յ20, Ϫ22Յ l Յ22
15037 / 8768 [R(int) ϭ 0.0553]
99.7 %
8768 / 0 / 456
1.041
0.16 ϫ 0.14 ϫ 0.12 mm
1.78 to 27.49°
Ϫ17Յ h Յ17, Ϫ10Յ k Յ11, Ϫ18Յ l Յ18
6948 / 3998 [R(int) ϭ 0.0575]
99.6 %
3998 / 0 / 224
1.016
R1 ϭ 0.0630, wR2 ϭ 0.1681
R1 ϭ 0.0533, wR2 ϭ 0.1324
R1 ϭ 0.1538, wR2 ϭ 0.2461
R1 ϭ 0.1140, wR2 ϭ 0.1753
Ϫ3
Ϫ3
0.697 and Ϫ1.148 eϪ
A
0.183 and Ϫ0.191 eϪ
A
˚
˚
1840
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 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1837Ϫ1841

[Cu(L1)2(py)2(H2O)](H2O) and [Cu(L2)2(py)2(H2O)]
[17] M. Gonzalez-Alvarez, G. Alzuet, J. Borras, L. de Castillo Agudo,
S. Garcia-Granada, J. M. Montejo Bernardo, J. Inorg. Biochem.
2004, 98, 189.
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