Cationic silver coordination compounds of polydentate ligands: Supramolecular structures of [Ag(Pzbp2Py)2(OSO 2CF3)] and [Ag2(Pzbp2Py) 2-(OSO2CF3)2</su

Article abstract of DOI:10.1002/ejic.200500231

The new silver complexes [Ag(Pz^bp2Py)₂(OSO ₂CF₃)], [Ag₂(Pz^bp2Py) ₂(OSO₂CF₃)₂], [Ag(Pz ^bpPy)₂(OSO₂CF₃)

Full text of DOI:10.1002/ejic.200500231

FULL PAPER
Cationic Silver Coordination Compounds of Polydentate Ligands:
Supramolecular Structures of [Ag(Pzbp2Py)2(OSO2CF3)] and [Ag2(Pzbp2Py)2-
(OSO2CF3)2] {Pzbp2Py = 2-[3,5-Bis(4-butoxyphenyl)pyrazol-1-yl]pyridine}
M. Luz Gallego,[a] Mercedes Cano,*[a] José A. Campo,[a] José V. Heras,[a] Elena Pinilla,[a,b]
M. Rosario Torres,[b] Pilar Cornago,[c] and Rosa M. Claramunt*[c]
Keywords: N ligands / NMR spectroscopy / Silver / Supramolecular chemistry
The new silver complexes [Ag(Pzbp2Py)2(OSO2CF3)],
[Ag2(Pzbp2Py)2(OSO2CF3)2], [Ag(PzbpPy)2(OSO2CF3)], [Ag3-
(TPzbp2Tz)(OSO2CF3)3] and [Ag3(TPzbpTz)(OSO2CF3)3] (5–9)
have been obtained by reaction of Ag(OSO2CF3) with the cor-
responding polydentate ligand 2-[3,5-bis(4-butoxyphenyl)pyr-
azol-1-yl]pyridine (Pzbp2Py, 1), 2-[3-(4-butoxyphenyl)pyrazol-
1-yl]pyridine (PzbpPy, 2), 2,4,6-tris[3,5-bis(4-butoxyphenyl)py-
razol-1-yl]-1,3,5-triazine (TPzbp2Tz, 3) and 2,4,6-tris[3-(4-bu-
toxyphenyl)pyrazol-1-yl]-1,3,5-triazine (TPzbpTz, 4), respec-
tively. The coordination effects induced on the 1H, 13C and
15N NMR chemical shifts of the complexes in solution and in
the solid state have been quantified, with the 15N NMR spec-
tra being used as a tool to establish the coordination site. All
complexes are consistent with an N,NЈ-chelating coordination
at each silver centre involving nitrogen atoms from pyrazole
and pyridine groups for 5 and 7 or from pyrazole and triazine
groups for 8 and 9. An additional Ag···OSO2CF3 interaction
completes the environment around the silver atom, giving rise
to a five-coordination or a three-coordination for complexes 5
and 7 and 8 and 9, respectively. The X-ray structures of 5 and
6 confirm the presence of the N,NЈ-chelating coordination of
the Pzbp2Py ligands and the coordinative participation of the
CF3SO3 counterion in the metal environment. The Ag···η2-ar-
ene bonds between neighbouring units in 6 are responsible
for the dimers containing four-coordinate silver atoms. At a
supramolecular level, Ag···O, C–H···O or C–H···F interactions
generate a 2D network in both compounds.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
–
–
counterions, NO3 , BF4– or CF3SO3 , giving rise to 1D, 2D
and 3D networks through hydrogen-bonding interactions
between the counterion and the cationic fragment. Hydro-
gen bonds involving the H-atom of the pyrazole ligand and
some other non-classical hydrogen-bonding interactions
were responsible for the networks of different dimensional-
ity.[3–5]
Introduction
Cationic silver() coordination compounds containing N-
donor ligands have extensively been described as producing
supramolecular arrays of different dimensionality in the so-
lid, this fact being related with the coordinative versatility
of the silver atom to adopt several coordination numbers
and with the variety of N-donor ligands and counter-
ions.[1,2]
On this basis, we thought that related polydentate ligands
based on the pyridine or triazine cores and pyrazole groups
as substituents (in which the NH is absent) should be candi-
dates for supramolecular arrays of metallic complexes
centred on coordinative bonds or coordinative interactions.
There are several examples described in the literature of
supramolecular networks based on a silver centre and dif-
ferent types of N-donor ligands.[1,6]
In previous papers we began to study the molecular as-
semblies produced by silver or gold coordination to substi-
tuted pyrazole ligands (HPzR2). The cationic coordination
compounds containing monodentate HPzR2 ligands [HPzR2
= 3,5-bis(butoxyphenyl)pyrazole (HPzbp2), 3,5-dimethyl-4-
nitropyrazole (HPzNO )] were bonded to their respective
2
We present here our studies of new silver complexes con-
taining the polydentate ligands 2-[3,5-bis(4-butoxyphenyl)-
pyrazol-1-yl]pyridine (Pzbp2Py, 1), 2-[3-(4-butoxyphenyl)pyr-
azol-1-yl]pyridine (PzbpPy, 2), 2,4,6-tris[3,5-bis(4-butoxy-
phenyl)pyrazol-1-yl]-1,3,5-triazine (TPzbp2Tz, 3) and 2,4,6-
tris[3-(4-butoxyphenyl)pyrazol-1-yl]-1,3,5-triazine (TPzbpTz,
4; Scheme 1). The silver compounds 5–9 were obtained by
treatment of Ag(OSO2CF3) with the respective polydentate
ligand. These new complexes exhibit variable environments
around the metal centre in which the nitrogen atoms of the
[a] Departamento de Química Inorgánica I, Facultad de Ciencias
Químicas, Universidad Complutense,
28040 Madrid, Spain
Fax: +34-91-394-4352
E-mail: mmcano@quim.ucm.es
[b] Laboratorio de Difracción de Rayos-X, Facultad de Ciencias
Químicas, Universidad Complutense,
28040 Madrid, Spain
[c] Departamento de Química Orgánica y Bio-Orgánica, Facultad
de Ciencias, UNED,
28040 Madrid, Spain
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
4370
© 2005 Wiley-VCH VeErluarg. GJ.mInboHrg.&CCheom. .K2G0a0A5,,4W37e0in–h4e3i8m1

Cationic Silver Coordination Compounds of Polydentate Ligands
FULL PAPER
polydentate PzPy and PzTz units and the oxygen atoms anion, as well as coordinative Ag···O and Ag···η2-arene and
–
from the counterion CF3SO3 are involved. In particular, other non-coordinative C–H···F, C–H···O, or π···π interac-
an additional Ag···η2-arene interaction is also established tions, will be discussed.
for 6 (Scheme 2). The structures of the complexes are sup-
ported by multinuclear magnetic resonance studies and, in
the cases of 5 and 6, by X-ray crystallography. Formation Results and Discussion
of one- and multidimensional networks through the inter-
connection of metallic centres by the inorganic CF3SO3
–
Syntheses of Ligands and Silver(I) Complexes
The synthesis of 2-[3-(4-butoxyphenyl)pyrazol-1-yl]pyri-
dine (PzbpPy, 2) and 2,4,6-tris[3-(4-butoxyphenyl)pyrazol-1-
yl]-1,3,5-triazine (TPzbpTz, 4) was achieved by reaction of
the sodium salt of 3-(4-butoxyphenyl)propane-1,3-dione
with hydrazinopyridine and the sodium salt of 3-(4-butoxy-
phenyl)pyrazole with 2,4,6-trichlorotriazine, respectively, by
similar procedures to those of the related compounds 2-
[3,5-bis(4-butoxyphenyl)pyrazol-1-yl]pyridine (Pzbp2Py, 1)
and
2,4,6-tris[3,5-bis(4-butoxyphenyl)pyrazol-1-yl]-1,3,5-
triazine (TPzbp2Tz, 3) previously described by us.[4,7]
Silver complexes 5–9 were obtained by combining the in-
organic salt Ag(OSO2CF3) with ligands 1–4 in different
stoichiometries, giving rise to monometallic [Ag(Pzbp2Py)2-
(OSO2CF3)] (5) and [Ag(PzbpPy)2(OSO2CF3)] (7) (from
1:2), dimetallic [Ag2(Pzbp2Py)2(OSO2CF3)2] (6) (from 1:1)
or trimetallic [Ag3(TPzbp2Tz)(OSO2CF3)3] (8) and
[Ag3(TPzbpTz)(OSO2CF3)3] (9) (from 3:1) complexes.
Scheme 2 shows the molecular characteristics of the three
types of compounds. A more detailed description of trime-
tallic complexes 8 and 9 is given in Scheme 3.
Scheme 1. Polydentate ligands used in this work, with the atomic
numbering used for the NMR discussion.
Scheme 3. Schematic representation of trimetallic compounds 8
and 9.
The IR spectra of the new complexes 5–9 were recorded
in KBr in the 4000–400 cm–1 range. For comparative pur-
poses, the IR spectra of the free ligands were also obtained.
The new complexes exhibit the characteristic bands of the
ligands, slightly modified by coordination. Compounds 5
and 6 were also characterised by X-ray diffraction and show
Ag–O distances of 2.704(8) and 2.325(6) Å, respectively, as
will be described below. The former one could be consid-
ered
to
be
a
coordinative
Ag···O
interac-
tion[1c,1f,1g,1i,1l,1m,6a,8] or even an Ag–O bond, as has been
reported by some authors,[1h,1m,9] whereas the latter is
clearly characteristic of an Ag–O bond.[1i,1k,10] The IR spec-
tra of 5 and 6 show absorption frequencies at 1273 and
Scheme 2. The complexes and their corresponding coordination en-
vironments described in this work.
Eur. J. Inorg. Chem. 2005, 4370–4381
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4371

M. Cano, R. M. Claramunt et al.
FULL PAPER
1288 cm–1, respectively, assigned to νas(SO3).[11] Thus, the ones are shifted downfield in relation to the free ligand (spe-
νas(SO3) values for related compounds are tentatively used cially noted in 6), except the H3Ј signal, which is shifted
to differentiate between interactions and/or covalent bonds. upfield by about 0.5 ppm. In contrast, the environment of
Following these results, the νas(SO3) absorption at the aromatic C6H4 protons is not significantly modified,
1290 cm–1 in 8 suggests a strong Ag···O interaction. The thus indicating that metal–arene interactions do not exist in
related complex 9 exhibits a broad band centred at solution.[2e,2f,12]
1253 cm–1, characteristic of the ligand, which could mask
When comparing the H NMR spectra of [Ag(PzbpPy)2-
(OSO2CF3)] (7) with that of 5, very close chemical shifts
are observed for the signals of the pyridine protons H5Ј and
H6Ј, whereas for the signals of H3Ј and H4Ј the shift upon
complexation is larger in complex 5.
1
the νas(SO3) absorption.
Multinuclear Magnetic Resonance Spectroscopy
The 1H NMR spectroscopic data of the ligands and their
Complexes
[Ag3(TPzbp2Tz)(OSO2CF3)3]
(8)
and
complexes are gathered in Tables 1 and 2.
[Ag3(TPzbpTz)(OSO2CF3)3] (9) present analogous 1H NMR
1
The H NMR spectra of [Ag(Pzbp2Py)2(OSO2CF3)] (5) spectra, the only differences coming from the pyrazole moi-
and [Ag2(Pzbp2Py)2(OSO2CF3)2] (6) show all the expected eties. This fact suggests similar three-coordinate silver envi-
resonances of the Pzbp2Py units. In both cases, as expected, ronments by considering the chelating complexation
an inequivalence of the substituents at the 3- and 5-posi- through the nitrogen atoms of the pyrazole and triazine
tions of the pyrazole ring is observed, in agreement with rings (N-Pz and N-Tz) and the Ag···OSO2CF3 interaction
the lack of symmetry. This fact is reflected by the presence proposed above from their IR spectra. Complex 8 exhibits
of two sets of signals for the OCH2 groups and the aromatic two different types of signals for the aromatic protons Ho
Ho and Hm protons of the substituents. In solution, the two and Hm, the first set is broad and the second one shows
Pzbp2Py ligands appear to be equivalent in both complexes, sharp multiplets. An analogous behaviour is found for the
as deduced from the unique signals observed for the H4 4-butoxyphenyl substituent in complex 9. The broadness of
proton and the pyridine protons. The signals of the latter the signals in both complexes can be explained on the basis
1
Table 1. H NMR chemical shifts (δ in ppm) and coupling constants (J in Hz) of the pyrazole moiety in compounds 1–9.[a]
aCH3
bCH2
cCH2
OCH2
Hm
Ho
H4
H5
Compound
Solvent
(pyrazole moiety)
1
0.98 (t)
3J = 7.4
0.99(t)
1.51 (m)
1.51 (m)
1.78 (m)
1.80 (m)
3.97 (t)
3J = 6.5
4.01 (t)
3J = 6.5
4.01 (t)
3J = 6.5
6.84 (m)
6.95 (m)
6.84 (m)
7.21 (m)
7.86 (m)
7.85 (m)
6.71 (s)
CDCl3
(Pzbp2
)
3J = 7.4
0.99 (t)
3J = 7.4
2
6.71 (d)
8.57 (d)
CDCl3
3J = 2.6
3J = 2.6
(Pzbp
)
3
0.94 (t)
3J = 7.4
1.01 (t)
3J = 7.4
1.00 (t)
3J = 7.4
1.43 (m)
1.51 (m)
1.51 (m)
1.72 (m)
1.82 (m)
1.79 (m)
3.87 (t)
3J = 6.6
4.04 (t)
3J = 6.5
4.00 (t)
3J = 6.5
6.85 (m)
6.98 (m)
6.97 (m)
7.24 (m)
7.76 (m)
7.91 (m)
6.63 (s)
CDCl3
(Pzbp2
)
4
6.77 (d)
8.71 (d)
CDCl3
3J = 2.9
3J = 2.9
(Pzbp
)
5
0.93 (t)
3J = 7.4
1.00 (t)
3J = 7.4
0.92 (t)
3J = 7.3
1.00 (t)
3J = 7.3
0.96 (t)
3J = 7.4
1.40 (m)
1.53 (m)
1.66 (m)
1.81 (m)
3.77 (t)
3J = 6.5
4.04 (t)
3J = 6.5
3.79 (t)
3J = 6.3
4.09 (t)
3J = 6.3
3.88 (t)
3J = 6.5
6.67 (m)
6.98 (m)
7.64 (m)
7.28 (m)
6.76 (s)
CD2Cl2
(Pzbp2
)
6
1.29–1.88 (m)
1.29–1.88 (m)
6.76 (d)
3J = 8.8
7.06 (d)
3J = 8.8
6.67 (m)
7.35 (d)
3J = 8.8
7.76 (d)
3J = 8.8
7.72 (m)
6.98 (s)
CD3COCD3
(Pzbp2
)
7
1.46 (m)
1.72 (m)
6.94 (d)
8.51 (d)
CD2Cl2
3J = 7.5
3J = 7.0
3J = 2.8
3J = 2.8
(Pzbp
)
8
0.93 (t)
3J = 6.9
1.03 (t)
3J = 6.6
0.90 (t)
3J = 7.2
1.41 (br)
1.55 (br)
1.38 (br)
1.67 (br)
1.83 (br)
1.62 (br)
3.85 (br)
4.04 (br)
3.88 (br)
7.01 (m)
7.14 (br)
6.88 (br)
7.46 (m)
7.71 (br)
7.88 (br)
6.67(s)
CDCl3
(Pzbp2
)
9
7.05 (br)
9.10 (br)
CD3COCD3
(Pzbp
)
[a] See Scheme 1 for numbering.
4372
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Eur. J. Inorg. Chem. 2005, 4370–4381

Cationic Silver Coordination Compounds of Polydentate Ligands
FULL PAPER
Table 2. 1H NMR chemical shifts (δ in ppm) and coupling con- well-defined signals. In contrast, the R1 substituent at the
stants (J in Hz) of the pyridine nucleus in compounds 1, 2 and 5–
3-position will be strongly affected by this equilibrium; this
causes a broadening of its signals. Dynamic experiments
7.[a]
H3Ј
H4Ј
H5Ј
H6Ј
were undertaken, but unfortunately they proved to be in-
conclusive. A similar explanation was provided for a related
case in a previous paper.[4]
Compound
Solvent
1
7.50 (d)
7.70 (ddd)
3J = 8.1
3J = 7.5
4J = 1.8
7.80 (ddd)
3J = 8.3
3J = 7.4
7.19 (m)
8.41 (m)
CDCl3
3J = 8.1
2
8.08 (ddd)
7.19 (ddd) 8.41 (ddd)
CDCl3
3J = 8.3
3J = 7.4
3J = 4.9
3J = 4.9
4J = 1.8
5
4J = J =
0.9
4J = 1.8
4J = 1.0
5J = 0.8
5
6.95 (br)
7.72 (ddd)
7.35 (dd) 8.41 (dd)
3
CD2Cl2
3J = J = 7.9
3J = 7.4
3J = 5.1
7.60 (m)
3J = 5.1
4J = 1.6
8.81 (m)
4J = 1.6
6
7.14 (d)
7.99 (ddd)
CD3COCD3 3J = 8.3
3J = J = 8.3
3
4J = 1.7
8.08 (ddd)
3J = 8.5
3J = 7.4
4J = 1.7
7
7.89 (d)
7.35 (ddd) 8.28 (ddd)
CD2Cl2
3J = 8.5
3J = 7.4
3J = 5.1
4J = 0.7
3J = 5.1
4J = 1.7
5J = 0.9
Scheme 4. Hypothetical equilibrium in solution for 8 and 9.
Table 3 shows the 15N NMR chemical shifts of ligands
1–4 in CDCl3 solution. Those corresponding to complexes
5–9 were recorded in solution and/or the solid state, where
[a] See Scheme 1 for numbering.
of a hypothetical equilibrium between two forms (a and b), no fluxional processes would occur. We have already dem-
as represented in Scheme 4. These forms should present an onstrated that 15N NMR spectroscopy is the most useful
asymmetric metal environment produced by a closer ap- tool for establishing the coordination site, as the increase in
proach to one of the two different coordinated nitrogen the nitrogen shielding on metal complexation reflects the
atoms (N-Tz or N-Pz). In this way, the environment of the changes in the paramagnetic shielding term.[4,13]
R2 substituent at the 5-position should not be appreciably
In complexes 5 and 7, it is clear that both the pyridine
modified when moving from a to b, therefore it gives rise to N1Ј and the pyrazole N2 bind to the metal atom as the
Table 3. 15N NMR chemical shifts (δ in ppm).[a] The silver coordination effects on the chemical shifts [∆δ(15N) = δ(15N)complex – δ(15N)
ligand] are given in brackets.
N-pyrazole (N-Pz)
N2
N-pyridine (N-Py)
N1Ј
N-triazine (N-Tz)
N1Ј,N3Ј,N5Ј
N1
Compound
Solvent
1
–166.0
–160.0[b]
–169.0[b,c]
–163.0[b,c]
–172.0
–85.0
–93.0[b]
–84.0
CDCl3
2
–105.0[b]
CDCl3
3
–86.0[b]
–156.8[b,c]
–177.0[c]
CDCl3
4
–93.4[b]
CDCl3
5[b]
–108.0 (–23)
–118.0 (–34)
CD2Cl2
5
–167.0
–171.0
–168.0
–97.0 (–12)
–105.0 (–20)
–105.0 (–12)
–112.0 (–28)
–119.0 (–35)
–129.0 (–24)
CPMAS
7[b]
CD2Cl2
7
–163.0
–168.0
–161.0
–114.0 (–21)
–120.0 (–27)
–130.0 (–44)
–128.0 (–23)
–130.0 (–25)
CPMAS
8[c]
–192.0 (–35.2)
–195.0 (–38.2)
–191.0 (–14)
CDCl3
8
CPMAS
9
CPMAS
–173.0
–165.0
–125.3 (–39.3)
–123.0 (–29.6)
[a] See Scheme 1 for numbering. [b] (1H-15N) gs-HMBC and gs-HMQC spectra. [c] Inverse gated spectra.
Eur. J. Inorg. Chem. 2005, 4370–4381
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4373

M. Cano, R. M. Claramunt et al.
FULL PAPER
chemical shifts of their signals move upfield with respect to This result is in agreement with the proposed asymmetric
the free ligands 1 and 2 [∆δ(15N) = δ(15N)complex – δ(15N) silver environment for the complexes.
ligand]. In the solid state, the asymmetry of the PzPy units
On the other hand, the chemical shift value of N1 of the
binding the silver cation in the crystal accounts for the two pyrazole in all complexes is not significantly affected by the
signals observed for each nitrogen. The X-ray structure of metal coordination, as expected due to the absence of its
5, which will described below, supports the above sugges- participation in coordination to the metal atom.
tion.
The 13C NMR spectroscopic data for all complexes in
When dealing with the data for 8 and 9 in comparison solution and the solid state (Table 4 and Table S1 in the
with those for 3 and 4, the coordination effects [∆δ(15N)] Supporting Information) are also in agreement with the
on the triazine N atoms and the pyrazole N2 atom are also proposed structures. The chemical shifts have been analysed
negative (Table 3). However, for 5 and 7 the ∆δ value for relative to those of the corresponding ligands and the main
N-Py is higher than that for N-Pz, while the opposite is conclusions are: (a) the chemical shifts of the carbon signals
observed for 8 and 9. These results agree with a higher of the 4-butoxyphenyl chains are not shifted upon coordi-
crowding of the N-Tz than that of the N-Py.
nation, (b) a downfield coordination shift of the C4 signal
The 15N NMR spectra of 8 in solution show a higher of around +3.5 ppm occurs, (c) the downfield shift of the
coordination shift for the N2 of the pyrazole than that for pyridine carbon signals follows the order C4Ј (+2.5 ppm) Ͼ
the nitrogen atoms of the triazine, which could be related C6Ј Ϸ C5Ј (+2.0 ppm) Ͼ C3Ј (+0.6 ppm), with the C2Ј sig-
to the greater strength of the Ag–N bond with the pyrazole. nal showing an upfield shift of 2.5 ppm, (d) an upfield coor-
Table 4. 13C NMR chemical shifts (δ in ppm) and coupling constants (J in Hz) of the pyrazole, pyridine and triazine moieties of
compounds 1–9.[a]
C3
C4
C5
C2Ј
C3Ј
C4Ј
C5Ј
C6Ј
Compound
Solvent
1
152.4
2J = 4.1
3J = 4.1
3J = 4.1
154.0
105.5
144.9
2J = 7.6
3J = 3.8
3J = 3.8
128.5
152.7
118.9
138.0
122.1
148.5
1J = 180.7
2J = 3.7
3J = 7.4
148.2
CDCl3
1J = 174.6
3J = 11.9
3J = 9.3
1J = 166.3
1J = 162.6
1J = 164.9
2
105.3
151.9
112.7
138.9
121.3
1J = 165.2
2J = 7.3
3J = 7.3
CDCl3
2J = 4.1
3J = 8.3
3J = 4.1
3J = 4.1
154.3
1J = 175.6
2J = 8.7
1J = 191.7
2J = 9.2
3J = 10.4
3J = 10.4
1J = 169.4
3J = 6.8
1J = 162.5
3J = 6.6
1J = 180.7
2J = 4.1
3J = 7.3
3
109.4
147.8
2J = 8.1
3J = 4.0
3J = 4.0
131.8
164.5
162.9
164.5
162.9
164.5
CDCl3
2J = 3.7
3J = 3.7
3J = 3.7
157.0
1J = 175.5
4
107.7
162.9
CDCl3
2J = 4.1
3J = 4.1
3J = 4.1
154.0
1J = 177.6
1J = 194.9
2J = 9.0
5
108.6
146.8
150.1
119.2
140.1
1J = 166.3
2J = 6.5
3J = 6.5
143.5
124.0
1J = 168.7
2J = 6.8
3J = 6.8
124.5
150.5
1J = 184.5
2J = 3.3
3J = 7.6
152.0
CD2Cl2
2J = 4.0
3J = 4.0
3J = 4.0
152.6
1J = 178.2
2J = 7.8
3J = 4.0
2J = 10.2
3J = 10.2
1J = 170.4
2J = 7.1
5
107.8
109.6
145.1
150.1
119.5
CPMAS
7
153.6
154.8
108.6
131.0
149.4
113.6
141.7
123.4
1J = 168.7
2J = 6.7
3J = 6.7
149.7
1J = 184.0
3J = 7.2
2J = 4.3
CD2Cl2
2J = 4.0
3J = 8.2
3J = 4.0
3J = 4.0
152.4
1J = 180.4
2J = 7.4
1J = 191.8
2J = 8.8
3J = 10.1
3J = 10.1
1J = 169.7
3J = 7.0
1J = 166.1
7
107.3
109.9
132.1
148.0
146.8
148.9
161.7
112.1
114.5
137.2
138.6
161.7
123.4
149.5
151.0
161.7
CPMAS
8
156.2
112.6
CDCl3
1J = 182.7
115.3
8
154.3
155.8
158.7 (br)
148.2
161.5
162.1
161.5
162.1
161.5
162.1
CPMAS
9
111.1
1J = 181.5
2J = 7.2
110.0
134.4 (br)
CD3COCD3
9
156.0
156.6
135.3
138.8
161.5
161.5
161.5
CPMAS
112.7
[a] See Scheme 1 for numbering.
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Cationic Silver Coordination Compounds of Polydentate Ligands
FULL PAPER
dination shift of the signals of the three equivalent triazine Table 5. Selected bond lengths [Å] and angles [°] for 5 and 6.
carbon atoms takes place.
5
The 13C NMR spectra in solution show the equivalence
Ag–N1
Ag–N3
Ag–N4
2.359(8) N6–Ag–N1
2.385(9) N6–Ag–N3
2.574(8) N1–Ag–N3
2.251(8) N6–Ag–N4
2.704(8) N1–Ag–N4
N3–Ag–N4
152.5(3)
136.6(3)
70.9(3)
69.7(3)
93.3(3)
128.2(3)
94.3(3)
77.5(3)
154.3(3)
93.1(3)
of the pyrazole groups, as well as the inequivalence of their
substituents, as already deduced by 1H NMR spectroscopy.
In the case of [Ag(Pzbp2Py)2(OSO2CF3)] (5), the 13C Ag–N6
Ag···O5
CPMAS NMR spectroscopic data indicate that both
Pzbp2Py ligands are inequivalent as well as the two 4-bu-
toxyphenyl groups of each ligand, as has also been estab-
lished by X-ray crystallography. The splitting of the signals
observed in all compounds in the solid state can also be
attributed to packing effects.
N1–Ag···O5
N3–Ag···O5
N4–Ag···O5
N6–Ag···O5
6
The above results establish a bidentate coordination in-
volving the N-Pz/N-Py in complexes 5 and 7 or N-Pz/N-Tz
Ag–N3
in 8 and 9. A new coordinative position around the silver Ag–O3
should be occupied by the oxygen atom from the triflate
CF3SO3 groups, giving rise to five-coordinate species con-
taining two PyPz ligands for 5 and 7, while three-coordina-
tion is proposed for 8 and 9.
In the search for additional structural information, the
X-ray structures of 5 and 6 were solved, and the results are
described in the following section.
Ag–N1
2.584(6) N3–Ag–O3
2.307(6) N3–Ag–N1
142.4(2)
69.4(2)
103.4(2)
116.3(2)
101.5(3)
104.9(2)
2.325(6) O3–Ag–N1
Ag–C25[a]
2.670(7) N3–Ag–C25C26[b]
2.706(7) O3–Ag–C25C26[b]
2.598(1) N1–Ag–C25C26[b]
Ag–C26[a]
Ag–C25C26[b]
[a] –x + 1, –y + 1, –z + 1. [b] C25C26 means the centroid of the
C25–C26 bond.
The C6H4 group at the 3-position in one molecule of 5
is almost parallel to the C6H4 group at the 5-position of the
other molecule [dihedral angle of 4.2(3)°], and the remain-
ing aryl rings are orthogonal between them [86.7(2)°] with
Crystal and Molecular Structures of 5 and 6
Compounds 5 and 6 crystallised from dichloromethane the butoxy chains in an opposite and almost symmetrical
solutions. Table 5 provides a selected list of bond lengths disposition. The four chains produce a crowding in one cor-
and angles.
ner of the metal environment. As a consequence, the silver
As depicted in Figure 1, the silver centre in 5 is four- centre has a deprotected position that allows the approach
coordinate with the nitrogen atoms of two Pzbp2Py ligands of an oxygen atom of the triflate group. The Ag···O5 dis-
in a distorted tetrahedral environment. This is reflected in tance of 2.704(8) Å is smaller than the sum of the
the dihedral angle formed by the AgN1N3 and AgN4N5 van der Waals radii of 2.84 Å.[14b] Similar values have been
planes of 124.8(2)°. The Ag–N bond lengths fall in the attributed to metal–oxygen bonds.[1h,1m,9] Therefore, the dis-
range of 2.28–2.50 Å found for related com- tance observed for 5 can be considered a “strong” coordina-
pounds.[1b,1h,1k,6e,6f,14] The mean Ag–N distance involving tive interaction, giving rise to a distorted trigonal bipyrami-
the N-Py atoms [2.318(8) Å] is shorter than that of the N-Pz dal geometry around the metal atom.
atoms [2.467(8) Å]. The largest distortion from tetrahedral
Because of the usually found three-coordination around
geometry is given by the N–Ag–N bite angle [N1–Ag–N3: the silver centre, we thought that the coordination of the
70.9(3)°; N6–Ag–N4: 69.7(3)°] associated with the chelating triflate group could be assessed by using a ratio of Pzbp2Py
ligands.
ligand/Ag(OSO2CF3) = 1.
Figure 1. ORTEP plot of 5 with ellipsoids at 40% probability, showing the Pzbp2Py coordination and the Ag···O intermolecular bonds.
Hydrogen atoms and the labelling of some atoms have been omitted for clarity.
Eur. J. Inorg. Chem. 2005, 4370–4381
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Figure 2. ORTEP plot of 6 with ellipsoids at 35% probability level, showing the dimeric unit formed by Ag···arene interactions. Hydrogen
atoms and the labelling of some atoms have been omitted for clarity.
The molecular structure of 6 is shown in Figure 2 and bonding of an arene ligand.[16a] In addition, the positional
corresponds to a dimeric entity produced by Ag···π(aryl parameters β and ∆ (where ∆ and β measure the deviation
ring) interactions between two molecules that are symmetri- from the centroid axis;[16a] see Scheme 5) of the silver centre
cally related by an inversion centre. The coordination geom- of 30.9° and 1.54 Å, respectively, are in agreement with the
etry around each silver atom in 6 is quite different from range of other structures showing an η2-coordination of the
that in 5. Thus, the metal atom in 6 adopts the usual three- arene.[16a] All the above arguments allow us unequivocally
coordination with the silver cation being trigonally coordi- to establish the presence of a dimerisation through an η2-
nated by the two nitrogen atoms of the bidentate Pzbp2Py Ag···π arene bond.
ligand and an oxygen atom from the triflate anion. The Ag–
N1 and Ag–N5 distances of 2.584(6) and 2.307(6) Å,
respectively, are almost equivalent to those found in 5. The
metal atom deviates 0.741(1) Å from the plane defined by
the three coordinated atoms (N1, N3, O), this deviation be-
ing produced by the proximity of an aryl group from the
Scheme 5. ∆ and β parameters for Ag···arene interactions.[16a]
second molecule, to which the silver atom is also coordi-
nated by an Ag···π bond,[15] thus generating a distorted tet-
rahedral environment. The short Ag–C distances [mean
In the crystal structures of 5 and 6 shown in Figures 3–
value of 2.668(7) Å] are in the range found in other com- 6, the triflate anion intervenes in the organisation around
pounds containing η2-Ag···π arene interactions (2.40– the [Ag(Pzbp2Py)2O] and [Ag(Pzbp2Py)O] units, either coor-
2.75 Å).[9,16] The contacts of the silver atom with the other dinating or forming a covalent bond with the metal atom
aromatic carbon atom are greater than 3 Å [the shortest is in 5 and 6, respectively. Such an anion is also employed
Ag–C24 (–x + 1, –y + 1, –z + 1) with 3.22(3) Å], consisting to expand the supramolecular environment with one of the
of an asymmetric coordination of the silver atom with the remaining oxygen atoms interacting with the silver centre
two carbon atoms of the benzene ring. The separation of or carbon atoms of neighbouring units. Thus, the coordina-
each silver atom from the mean plane of its coordinated tion of the anion in 6, or strong interaction in 5, can be
aryl group of 2.567(5) Å lies in the range inherent to the considered as the first stage of the supramolecular organi-
Figure 3. View of the strand along the b axis in 5, showing the Ag···O, C–H···O and C–H···F contacts.
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Cationic Silver Coordination Compounds of Polydentate Ligands
FULL PAPER
Figure 4. View of the double strand along the b axis in 6, showing the Ag···O contacts between dimers.
Figure 5. View of a layer parallel to the (101) plane of the 2D network of 5.
sation, while the next one is consistent with the assembly ½ + 1, y – ½, –z + ½: 3.24(2) Å] and C16···F2 [–x + ½ +
of [Ag(Pzbp2Py)2O] and [Ag(Pzbp2Py)O] units, which can be 1, y – ½, –z + ½: 3.04(2) Å] interactions (Figure 3). In 6,
described as follows:
the overall arrangement consists of a double strand along
i) The oxygen atoms of the triflate, which are not involved the b axis in which two triflate anions act as bridging
in a direct bond or interaction with the silver atom, are groups of each neighbouring dimer [Ag1···O5 (–x + 1, –y
bonded to a pair of adjacent molecules by Ag···O or C– + 2, –z + 1): 2.84(1) Å; Ag1···O4 (–x + 1, –y + 2, –z +
H···O/F interactions, thus generating strands. In 5, the 1): 3.32(1) Å; see Figure 4). In addition to related C–H···O
strands are defined along the b axis by the C22···O7 [–x + interactions [C10···O5 (–x + 1, –y + 2, –z + 1): 3.24(2) Å;
Eur. J. Inorg. Chem. 2005, 4370–4381
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M. Cano, R. M. Claramunt et al.
FULL PAPER
Figure 6. View of a layer parallel to the (001) plane of the 2D network of 6.
C25···O4 (x, y – 1, z): 3.18(2) Å], the strands are mainly
determined by a direct Ag···O bond. The triflate tecton in several features can be established as determining factors of
both 5 and 6 is responsible for the 1D arrangement. the supramolecular arrays: i) The structural role of the trifl-
From the comparative study of the structures of 5 and 6,
ii) New non-conventional hydrogen-bonding interactions ate anion takes place by coordination or strong interaction
involving the CF3 groups of the triflate group in 5 or bifur- of the silver centre to an oxygen atom (Ag···O); ii) the coor-
cated C–H···O interactions in 6 extend the supramolecular dination of the anion to the [Ag(Pzbp2Py)2]+ units in 5 is
arrangements into a 2D network. Thus, the C–H···F inter- less favoured than in 6 due to the crowding around the me-
actions between the chains in 5 [C58···F3 (x + ½, –y + ½ tal centre, which prevents the additional Ag···π interaction
+ 1, z – ½): 3.25(3) Å], where the F atoms proceed from that is responsible for the dimer in 6; iii) double or single
alternating and symmetrically disposed bridging triflate strands are built on the basis of hydrogen-bonding interac-
groups along the c axis of the chain, give rise to layers tions.
which lie parallel to the (101) plane (Figure 5). In 6, the
same oxygen atom implicated in the strand interacts with
the pyridine group of an adjacent strand [C8···O4 (–x, y +
2, –z + 1): 3.31(1) Å], thereby extending these interactions
through the (001) plane (Figure 6).
Experimental Section
Materials and Instrumentation: All commercial reagents were used
as supplied. 3-(4-Butoxyphenyl)pyrazole (HPzbp), 2-[3,5-bis(4-but-
oxyphenyl)pyrazol-1-yl]pyridine (Pzbp2Py, 1) and 2,4,6-tris[3,5-
bis(4-butoxyphenyl)pyrazol-1-yl]-1,3,5-triazine (TPzbp2Tz, 3) were
prepared according to the literature.[4,7,17] Commercial solvents
were dried prior to use. Elemental analyses for C, H, N, S were
carried out by the Microanalytical Service of the Complutense Uni-
versity. IR spectra were recorded with an FTIR Nicolet Magna-
550 spectrophotometer with samples as KBr pellets in the 4000–
400 cm–1 region. The exact mass of 4 was determined by high reso-
lution mass spectrometry at 70 eV using the electron impact mode
with a VG AutoSpec spectrometer.
Concluding Remarks
Silver() coordination complexes containing Pzbp2Py (1),
PzbpPy (2), TPzbp2Tz (3) and TPzbpTz (4) polydentate li-
gands have been obtained. An N,NЈ-bidentate coordination
has been established in [Ag(Pzbp2Py)2(OSO2CF3)] (5) and
[Ag(PzbpPy)2(OSO2CF3)] (7), which involves the N-Pz/N-
Py sites, and implicates the N-Pz/N-Tz ones in
[Ag3(TPzbp2Tz)(OSO2CF3)3] (8) and [Ag3(TPzbpTz)(O- NMR Parameters: Spectra were recorded at 298 K with a Bruker
SO2CF3)3] (9). A new coordinative position is occupied by
the oxygen atom from the triflate groups, giving rise to five-
DRX 400 spectrometer (400.13 MHz for H; 100.62 MHz for 13C;
1
40.56 MHz for 15N NMR), except for compound 6, where only the
1H NMR spectrum was registered with a Bruker AC 200 spectrom-
coordinate species containing two PzPy ligands for 5 and 7,
eter. Chemical shifts (δ in ppm) are given relative to internal sol-
while three-coordination is proposed for 8 and 9.
vents [CDCl3 (δ = 7.26 ppm), CD2Cl2 (δ = 5.32 ppm) and (CD3)2-
The compound [Ag2(Pzbp2Py)2(OSO2CF3)2] (6), which
CO (δ = 2.05 ppm) for 1H NMR; 13CDCl3 (δ = 77.0 ppm), CD2Cl2
contains Ag/Pzbp2Py in a 1:1 stoichiometric ratio, exhibits
(δ = 54.0 ppm) and (CD3)2CO (δ = 29.9 and 206.7 ppm) for 13C
the expected metal environment determined by the N,NЈ-
bidentate Pzbp2Py ligand and the oxygen atom of the triflate
group. However, in this case, this environment is expanded
NMR; external nitromethane (δ = 0.0 ppm) for 15N NMR]. Coup-
ling constants (J in Hz) are accurate to 0.2 Hz for 1H and 13C.
2D inverse proton detected heteronuclear shift correlation spectra,
through an M–π olefinic bond to give rise to dimeric units. 1H-13C gs-HMQC, H-13C gs-HMBC, H-15N gs-HMBC and H-
1
1
1
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Cationic Silver Coordination Compounds of Polydentate Ligands
FULL PAPER
15N gs-HMQC were recorded with the standard pulse sequences.[18]
Solid-state 13C (100.73 MHz) and 15N (40.60 MHz) CPMAS NMR
spectra were recorded with a Bruker WB-400 spectrometer at 300 K
using a 4-mm DVT probehead. Samples were carefully packed in
4-mm diameter cylindrical zirconia rotors with Kel-F end-caps. Op-
Synthesis of [Ag2(Pzbp2Py)2(OSO2CF3)2] (6): This compound was
prepared in a similar way to 5, from Ag(OSO2CF3) (35 mg,
0.14 mmol) and Pzbp2Py (1; 60 mg, 0.14 mmol). The product was
crystallised from a solution of dichloromethane at 4 °C. Yield:
38 mg (40%). C58H62Ag2F6N6O10S2 (1397.0): calcd. C 49.87, H
4.47, N 6.02, S 4.59; found C 49.82, H 4.57, N 5.93, S 4.56. IR
1
erating conditions involved 3.2-µs, 90° H pulses and a decoupling
field strength of 78.1 kHz with the TPPM sequence. 13C NMR
spectra were originally referenced to a glycine sample and then the
chemical shifts were recalculated relative to SiMe4 [for the carbonyl
atom: δ(glycine) = 176.1 ppm], and 15N spectra to 15NH4Cl and
then converted to the nitromethane scale using the relationship
δ(15N)MeNO2 = δ(15N)NH4Cl – 338.1 ppm. The typical acquisition
parameters for 13C CPMAS were: spectral width: 40 kHz; recycle
delay: 5 s; acquisition time: 30 ms; contact time: 2 ms; accumu-
lation number: 900–2200; spin rate: 12 kHz. In order to distinguish
protonated and unprotonated carbon atoms, the NQS (non-quater-
nary suppression) experiment by conventional cross-polarisation
was recorded; before the acquisition, the decoupler was switched
off for a very short time of 25 µs.[18] Those for 15N CPMAS were:
spectral width: 40 kHz; recycle delay: 5 s; acquisition time: 35 ms;
contact time: 6 ms; accumulation number: 80000–115000; and spin
rate: 6 kHz.
(KBr): ν = 1605 and 1572 cm–1 ν(C=N), 1288 νas(SO3), 1027
˜
νs(SO3).
Synthesis of [Ag(PzbpPy)2(OSO2CF3)] (7): The compound was pre-
pared in
a similar way to 5, from Ag(OSO2CF3) (87 mg,
0.34 mmol) and PzbpPy (2; 200 mg, 0.68 mmol). The product was
recrystallised from dichloromethane/hexane at 4 °C. Yield: 109 mg
(38%). C37H38AgF3N6O5S (843.7): calcd. C 52.68, H 4.54, N 9.96,
S 3.80; found C 52.49, H 4.47, N 9.95, S 3.81. IR (KBr): ν = 1608
˜
and 1578 cm–1 ν(C=N), 1249 νas(SO3), 1031 νs(SO3).
Synthesis of [Ag3(TPzbp2Tz)(OSO2CF3)3] (8): Ag(OSO2CF3)
(33.7 mg, 0.13 mmol) was added to a solution of TPzbp2Tz
(50.6 mg, 0.04 mmol) in 30 mL of dry THF. After 24 h of stirring,
the solution was filtered through a plug of Celite. The solvent was
then evaporated to about 5 mL, and pentane (10 mL) was added.
The yellow solid formed was filtered off, washed with small por-
tions of pentane and dried in vacuo. Yield: 40 mg (48%).
C75H81Ag3F9N9O15S3 (1939.3): calcd. C 46.45, H 4.21, N 6.50;
Synthesis of 2-[3-(4-Butoxyphenyl)pyrazol-1-yl]pyridine (PzbpPy, 2):
A solution of 4-butoxyacetophenone (1.81 g, 9.42 mmol) in ethyl
formate (1.16 mL, 14.13 mmol) and toluene (15 mL) was added to
a slurry of anhydrous sodium methoxide (0.51 g, 9.42 mmol) in tol-
uene (50 mL). A clear solution was obtained, which became a
slurry after 5 min. The solid was isolated by filtration after 2 h
at room temperature and washed with hexane. The solid obtained
(0.36 g, 1.48 mmol) was dissolved in 96% ethanol (10 mL), and
then treated with hydrochloric acid (ca. 2.5 mL, spec. grav. 1.18).
2-Hydrazinopyridine (0.65 g, 5.92 mmol) dissolved in the minimum
amount of 96% ethanol was added to this solution. The mixture
was refluxed for 3 h, and then the solvent was evaporated to about
half the original volume and the resulting solution kept in a refrig-
erator at 4 °C. Pale-yellow needles were obtained after 2 d, which
were filtered off and washed with hexane. Yield: 0.30 g (69%). M.p.
79 °C. C18H19N3O (293.37): calcd. C 73.70, H 6.53, N 14.32; found
found C 46.49, H 4.36, N 6.49. IR (KBr): ν = 1610 cm–1 ν(C=N),
˜
1253 νas(SO3), 1027 νs(SO3).
Synthesis of [Ag3(TPzbpTz)(OSO2CF3)3] (9): The compound was
prepared as described for 8, from TPzbpTz (31.4 mg, 0.04 mmol)
and Ag(OSO2CF3) (33.3 mg, 0.13 mmol). Yield: 41.2 mg (63%).
C45H45Ag3F9N9O12S3 (1494.7): calcd. C 36.16, H 3.03, N 8.43;
found C 36.34, H 3.41, N 8.38. IR (KBr): ν = 1610 cm–1 ν(C=N),
˜
1253 νas(SO3), 1027 νs(SO3).
X-ray Structure Determinations: Colourless thin plate or prismatic
single crystals of [Ag(Pzbp2Py)2(OSO2CF3)] (5) and [Ag2(Pzbp2
-
Py)2(OSO2CF3)2] (6), respectively, were grown from dichlorometh-
ane solutions. Data collection was carried out at room temperature
with a Bruker Smart CCD diffractometer using graphite-mono-
chromated Mo-Kα radiation (λ = 0.71073 Å) operating at 50 kV
and 20 mA. In all cases, data were collected over a hemisphere of
the reciprocal space by combination of three exposure sets. Each
exposure covered 0.3° in ω. The cell parameters were determined
and refined by a least-squares fit of all reflections collected. The
first 50 frames were recollected at the end of the data collection
to monitor crystal decay; no appreciable decay was observed. A
summary of the fundamental crystal and refinement data is given
in Table 6. The structures were solved by direct methods and re-
fined by full-matrix least squares on F2.[19] Anisotropic parameters
were used in the last cycles of refinement for all non-hydrogen
atoms, with some exceptions. Thus, some carbon atoms of the bu-
toxy chains, the fluorine and only two oxygen atoms of the triflate
C 73.61, H 6.45, N 14.25. IR (KBr): ν = 1616 and 1580 cm–1
˜
ν(C=N).
Synthesis of 2,4,6-Tris[3-(4-butoxyphenyl)pyrazol-1-yl]-1,3,5-tri-
azine (TPzbpTz, 4): NaH (95%, 63.9 mg, 2.53 mmol) was added to
a solution of HPzbp (438.5 mg, 2.03 mmol) in freshly distilled dry
THF (30 mL) under argon. After 1.5 h at 90 °C, the solution was
allowed to cool, and 2,4,6-trichlorotriazine (cyanuric chloride,
126.1 mg, 0.677 mmol) was added. The solution was heated at
90 °C for 11.5 h and at 60 °C for 15 h. The solvent was evaporated
and the residue chromatographed on 60-F254 silica gel with chloro-
form/acetonitrile (92:8) as eluent. Rf = 0.35. Yield: 122 mg (25%).
M.p. 197–199 °C. Exact mass calcd. for C42H45N9O3: 723.3645;
found 723.5. IR (KBr): ν = 1612 cm–1 ν(C=N).
˜
Synthesis of [Ag(Pzbp2Py)2(OSO2CF3)] (5): Ag(OSO2CF3) (45 mg, group were refined isotropically. The third oxygen atom of the trifl-
0.17 mmol) was added under nitrogen to a solution of Pzbp2Py (1;
153 mg, 0.34 mmol) in dry THF (40 mL). After 24 h of stirring, the
solution was filtered through a plug of Celite. Then, the solvent
was removed in vacuo and 10 mL of dichloromethane was added.
The solution was again filtered through a plug of Celite and con-
centrated. A colourless solid was isolated after addition of hexane
at 4 °C. The product was crystallised from a solution of dichloro-
methane and hexane at 4 °C. Yield: 111 mg (38%).
C57H62AgF3N6O7S (1140.1): calcd. C 60.05, H 5.48, N 7.37, S 2.81;
ate group, which interacts with the silver atom, was refined aniso-
tropically. Some of these atoms were refined with geometrical re-
straints and variable common carbon–carbon and carbon–oxygen
distances. Hydrogen atoms were included in calculated positions,
and refined as riding on their respective carbon atoms with thermal
parameters related to the bonded atoms. Hydrogen atoms were
analysed with SHELXS-97 and PARST97.[20] The largest residual
peaks in the final difference map were 1.173 and 1.266 eÅ–3 for 5
and 6, respectively, in the vicinity of the fluorine atoms. CCDC-
found C 59.65, H 5.34, N 7.34, S 2.78. IR (KBr): ν = 1612 and 266326 (5) and -266327 (6) contain the supplementary crystallo-
˜
1573 cm–1 ν(C=N), 1273 νas(SO3), 1028 νs(SO3).
graphic data for this paper. These data can be obtained free of
Eur. J. Inorg. Chem. 2005, 4370–4381
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Table 6. Crystal and refinement data for 5 and 6.
5
6
Empirical formula
Formula mass
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C57H62AgF3N6O7S
C58H62Ag2F6N6O10S2
1397.03
1140.06
monoclinic
P21/n
9.4058(6)
22.149(1)
26.704(2)
90
98.577(1)
90
5508.4(6)
4
triclinic
¯
P1
10.602(1)
10.912(1)
14.735(1)
72.466(2)
73.340(2)
72.473(2)
1513.6(4)
1
α [°]
β [°]
γ [°]
V [Å3]
Z
F(000)
2368
1.375
296(2)
0.471
0.45×0.25×0.05
φ and ω
–11,–24,–27 to 11,26,31
1.20–25.00
28738
9664 (Rint = 0.120)
9664/13/592
3211
1456
1.537
296(2)
0.796
0.28×0.17×0.05
φ and ω
–12,–12,–17 to 6,10,17
1.48–25.00
7954
5269 (Rint = 0.038)
5269/10/305
2965
Dcalcd. [gcm–3]
T [K]
µ(Mo-Kα) [mm–1]
Crystal size [mm]
Scan technique
Data collected
θ [°]
Refls. collected
Refls. indep.
Data/restraints/parameters
Refls. observed [I Ͼ 2σ(I)]
GOF (F2)
0.899
0.089
0.328
1.173
0.973
0.069
0.222
1.266
R(F)[a]
wR(F2) (all data)[b]
Largest residual peak [eÅ–3]
2
2 2
[a] Σ(|Fo| – |Fc|)/Σ|Fo|. [b] {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
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Acknowledgments
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Ministerio de Ciencia y Tecnología is gratefully acknowledged
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Received: March 17, 2005
Published Online: September 12, 2005
Eur. J. Inorg. Chem. 2005, 4370–4381
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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