The structural role of the triflate anion in the non-covalent silver polymer [Ag(LOH)2(CF3SO3)(CH3CN)] {LOH = α-(4-pyridyl)benzhydrol}

Article abstract of DOI:10.1002/ejic.200300929

Ag(CF₃SO₃) was reacted with the ligand α-(4-pyridyl)benzhydrol (LOH) in order to build a mixed organic/inorganic analogue of wheel-and-axle diols. In the resulting [Ag(LOH)₂(CF ₃SO₃)(CH₃CN)] complex, the metal is four-coordinate, with two pyridines trans each other and a triflate and an acetonitrile group completing a sawhorse geometry. The main structural motif is based on the strongest and most directional tectons, the coordination bond Ag-O and the hydrogen bonds -OH...O-S-O...HO-. Secondly, the sixfold phenyl embrace, CH₃...π, CH₃...CF₃ and Ag...F tectons also direct the crystal assembly. A new synthon originating from the combination of the S-O...HO-, the π...CH₃ and the CH₃...CF₃ individual tectons is identified. The structural roles of the anion and of the solvent are discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300929

SHORT COMMUNICATION
The Structural Role of the Triflate Anion in the Non-Covalent Silver Polymer
[Ag(LOH)2(CF3SO3)(CH3CN)] {LOH ؍ α-(4-Pyridyl)benzhydrol}
Alessia Bacchi,*[a] Elsa Bosetti,[a] Mauro Carcelli,[a] Paolo Pelagatti,[a] and
Dominga Rogolino[a]
Keywords: Crystal engineering / Non-covalent interactions / Hydrogen bonds / Molecular tectonics / Silver compounds
Ag(CF3SO3) was reacted with the ligand α-(4-pyridyl)benz- gen bonds −OH···O−S−O···HO−. Secondly, the sixfold phenyl
hydrol (LOH) in order to build a mixed organic/inorganic
analogue of wheel-and-axle diols. In the resulting [Ag-
embrace, CH3···π, CH3···CF3 and Ag···F tectons also direct
the crystal assembly. A new synthon originating from the
(LOH)2(CF3SO3)(CH3CN)] complex, the metal is four-coord- combination of the S−O···HO−, the π···CH3 and the CH3···CF3
inate, with two pyridines trans each other and a triflate and
an acetonitrile group completing a sawhorse geometry. The
main structural motif is based on the strongest and most dir-
individual tectons is identified. The structural roles of the an-
ion and of the solvent are discussed.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ectional tectons, the coordination bond Ag−O and the hydro- Germany, 2004)
Introduction
Our purpose is to incorporate a metal center into the L
spacer of the HOC(Ar)2-L-(Ar)2COH host framework, in
order to combine the clathrating nature of the diol organic
matrix with the potential host-guest reactivity triggered by
the inorganic functionality (Scheme 2). The coordination of
a metal center at the peripheral rim of the TPM molecule
could tune the electronic properties of the chromophore
and concomitantly drive the organization of the crystal
architecture.
We are currently pursuing the engineering of crystalline
systems built by combining photoactivatable triphenylmeth-
anol derivatives with metal centers structured in porous net-
works.
Scheme 1
Triphenylmethanol derivatives (TPMs) (Scheme 1) are ac-
tively studied because they show CϪOH photocleavage, ac-
companied by an intense chromatic change on irradiation
by UV/Visible light both in polar solvents and in the solid
state.[1] Furthermore, compounds with the general formula
Ar3XϪOH (X ϭ C, Si, Ge) have a propensity to crystallize
giving trimeric or tetrameric molecular aggregates based on
hydrogen-bonded ϪOH clusters, and they also frequently
form clathrate compounds with hydrogen-bond acceptor
solvent molecules.[2] Remarkable clathrating properties are
shown also by the diol derivatives of the general formula
HOC(Ar)2-L-(Ar)2COH, where L is a suitable rigid organic
spacer,[3a] the so-called ‘‘wheel-and-axle’’ systems.
Scheme 2
Our approach to the rational design of these architectures
is based on the molecular tectonics method,[4] in which the
crystal structure is deconvoluted in the contributions of the
single inorganic and organic building blocks, which are sep-
arately analyzed and optimized.
The first step in modeling these organic-inorganic
‘‘wheel-and-axle’’ complexes consists in the introduction of
a transition metal as a bridge between two aromatic rings;
this aim is pursued by synthesizing the transition metal
complexes of the ligand α-(4-pyridyl)benzhydrol (LOH,
Scheme 2).[5] Here, we report and analyze the solid-state ar-
rangement of the new silver complex [Ag(LOH)2-
[a]
Dipartimento di Chimica Generale ed Inorganica, Chimica
Analitica, Chimica Fisica, University of Parma,
Parco Area delle Scienze 17A, 43100 Parma, Italy
E-mail: alessia.bacchi@unipr.it
Eur. J. Inorg. Chem. 2004, 1985Ϫ1991
DOI: 10.1002/ejic.200300929
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1985

A. Bacchi, E. Bosetti, M. Carcelli, P. Pelagatti, D. Rogolino
˚
SHORT COMMUNICATION
(OTf)(CH3CN)], with the aim of establishing a hier- distance [2.650(9) A] is one of the longest ever observed in
archy in the importance and robustness of the supramolecu- the solid state for AgϪNϵCϪCH3 coordination. The Ag
lar motifs observed in the compound and of elucidating the atom, the CH3CN and CF3SO3 ligands are placed on a
structural role of the counteranion. Currently, we also re- symmetry plane that cuts the complex perpendicularly to
port our first results on the supramolecular organization of the NpyϪAgϪNpy vector.
ϩ
two Ag(LOH)2 complexes with weakly coordinating
In a related work,[6] we found that in [Ag(LOH)2]BF4 and
[Ag(LOH)2]PF6 the silver ion coordinates linearly two li-
Ϫ
Ϫ [6]
anions, BF4 and PF6
.
The analysis of the relevant interactions in the crystal gand molecules. In [Ag(LOH)2(CF3SO3)(CH3CN)], a new
packing of [Ag(LOH)2(OTf)(CH3CN)] will follow the element is introduced into the organization of the crystal
scheme: (i) search for hydrogen bonds involving the ϪOH structure around the [Ag(LOH)2]ϩ unit; namely, the metal
donor; (ii) search for short contacts (less than the sum of atom also employs covalent bonds to expand its supramol-
the van der Waals radii); among the above short contacts, ecular environment by directly coordinating the anion and
detect
weak
hydrogen
bonds,
π
interactions, the acetonitrile molecule. Scheme 3 shows the geometric
aromatic···aromatic association; (iii) heuristic search for descriptors chosen to represent the conformation of the
other supramolecular long range arrangements, such as complex. Selected parameters are: the dihedral angle be-
multiple phenyl embrace and long F···Ag contacts, to com- tween pyridines (ψ: C4ϪN1ϪN1ЈϪC4Ј), the orientation of
plete the metal environment; (iv) analysis of the combi- the CϪOH vectors with respect to the adjacent pyridine (ϕ:
nation of the patterns to determine recurrent motifs for the O1ϪC1ϪC2ϪC3 and O1ЈϪC1ЈϪC2ЈϪC3Ј), and the re-
ϩ
structure, in comparison also to other Ag(LOH)2 com- ciprocal orientation of the two CϪOH vectors (χ:
plexes.[6]
O1ϪC1ϪC1ЈϪO1Ј). The classification of the triaryl groups
has been made following Dance’s analysis of triphenyl-
phosphanes,[8] by calculating the torsion angles
Results and Discussion
C
(ortho)ϪC(ipso)ϪC(sp3)ϪO for each ring (labeled so that |tor-
sion| Ͻ 90°), and then considering the cases: rotor (20° Ͻ
|T1| ഠ |T2| ഠ |T3| Ͻ 70°, same sign), anti-rotor (20° Ͻ
|T1| ഠ |T2| ഠ |T3| Ͻ 70°, opposite sign), parallel flipper (|T1|
Ͻ 20°, T2 ഠ ϪT3), orthogonal flipper (70° Ͻ |T1| Ͻ 90°,
[Ag(LOH)2(OTf)(CH3CN)] is obtained by reacting LOH
with an excess of Ag(CF3SO3). The complex is stable in the
solid state in the dark, while its solution slowly releases sil-
ver. The spectroscopic characterization does not show any
1
remarkable feature: in the H NMR spectrum, the protons
H4 and H5 of the pyridyl ring are deshielded with respect to
the free ligand, and the singlet assigned to the acetonitrile
molecule is present (δ ϭ 2.00 ppm); in the IR spectrum,
there are the typical bands assigned to the triflate anion.
Crystals suitable for X ray diffraction analysis were ob-
tained from the mother liquor within a couple of days.
The metal is coordinated to two pyridine Npy atoms, one
oxygen atom of the anion and to one acetonitrile molecule
(Figure 1), in a sawhorse geometry already observed for
similar Ag complexes[7] [N2ϪAgϪO2 ϭ 127.7(4)°]. The
acetonitrile molecule is loosely bound, in fact the AgϪN2 Scheme 3
Figure 1. Molecular structure and labelling of the independent unit of [Ag(LOH)2(CF3SO3)(CH3CN)]; Ag, O2, S1, C19, F3, N2, C20
and C21 are on a mirror plane; phenyl C13ϪC18 is disordered over two orientations
1986
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Eur. J. Inorg. Chem. 2004, 1985Ϫ1991

The Structural Role of the Triflate Anion in a Non-Covalent Silver Polymer
SHORT COMMUNICATION
Table 1. Molecular conformation and supramolecular organization of the [Ag(LOH)2(OTf)(CH3CN)] complex; top: ψ ϭ reciprocal pyri-
dine orientation, ϕ ϭ orientation of the CϪOH vector relative to the adjacent pyridine ring, χ ϭ reciprocal orientation of the two CϪOH
vectors, T1, T2, T3 ϭ conformation of the triaryl group, following Dance;[8] T1 refers to the pyridine ring and T2 to the ring involved
in the NCϪCH3···π contact; T3 is presented for both disordered conformers (a) and (b); bottom: supramolecular tectons belong to
three classes: metal environment (4ϩ1 coordination), hydrogen bond (ϪOH···OϪSϪO···HOϪ motif), and weak directional interactions
[CH3···CF3, CH3···π, sixfold phenyl embrace (6PE)]; symmetry operations: (i) x, 3/2 Ϫ y, z; (ii) 1 Ϫ x, 2 Ϫ y, Ϫz; (iii) x ϩ 1, y, z; (iv)
x ϩ 1, y, z ϩ 1; (v) 2 Ϫ x, 2 Ϫ y, 1 Ϫ z; (vi) x, 5/2 Ϫ y, z; (vii) 2 Ϫ x, y Ϫ 1/2, 1 Ϫ z
Molecular
ψ
ϕ
χ
T1
T2
T3
conformation (°) (C4ϪN1ϪN1ЈϪC4Ј)
(O1ϪC1ϪC2ϪC3)
(O1ϪC1ϪC1ЈϪO1Ј)
0.00
Ϫ24.3(5)
0.00
Ϫ24.3(5)
Ϫ35.1(5)
Ϫ69.8(7)(a)
Ϫ38.0(8)(b)
Supramolecular
˚
organization (A,°)
Metal environment
H-bond
Weak directional interactions
AgϪNpy
Ag···O
Ag···Nsolv
Ag···CF3
OϪH···O
D···A
CH3···F
CH3···π
6PE
OϪC1Ar3···Ar3C1ϪO
ϽDHA
Ag···N1
Ag···O2
Ag···N2
Ag···F3(iii)
O1ϪH···O3(ii) C20···F3(iv) C20···C9(v) C1···C1(v)
2.191(3)
2.529(5)
2.650(9)
3.542(6)
2.849(5)
171(5)
3.00(1)
3.552(7)
6.535(7)
Ag···N1(i)
N1ϪAgϪO2
N1ϪAgϪN2
N1ϪAgϪF3(iii)
C20···C9(vii)O1ϪC1···C1(v)
2.191(3)
93.90(8)
90.86(9)
84.56(8)
3.552(7)
175.9(2)
N1ϪAgϪN1(i)
O2ϪAgϪN2
O2ϪAgϪF3(iii)
O1(v)ϪC1(v)···C1
168.7(2)
127.7(4)
117.3(2)
175.9(2)
N2ϪAgϪF3(iii)
115.0(3)
T2 ഠ ϪT3). Table 1 lists the results of the conformational
(ii) The short contacts (Table 1) involve the methyl group
analysis and contains the key features of the supramolecu- of the acetonitrile ligand, which is sandwiched between two
lar arrangement; symmetry operations cited in the text are aromatic rings giving two symmetric CH3···π[9] interactions
˚
˚
also reported in Table 1. The pyridine rings are coplanar [C20···C9(v,vii) ϭ 3.552(7) A, H20···C9(v,vii) ϭ 2.87 A,
˚
(Ψ ϭ 0°), while the ϪOH groups deviate by Φ ϭ Ϫ24.3(5)° H···π ϭ 2.76 A]. The two aromatic rings belong to a pair
from the pyridine plane. The complex exhibits the syn con- of triaryl groups in an adjacent double strand. The same
figuration for the two ϪOH groups (χ ϭ 0°), in contrast methyl group also interacts with the triflate bridging the
with the anti configuration usually found in similar two aryl groups by means of a CH3···CF3 interaction
cases;[6,13] this will be related to the crystal packing in the [C20···F3(iv) ϭ 3.00(1) A]. Both interactions connect the
˚
course of the discussion. The triaryl group has a regular double strands in a sheet (Figure 3). A short non-bonded
˚
rotor conformation, with T1, T2 and T3 values falling in H···H(vi) distance (2.36 A, vi ϭ x, 5/2 Ϫ y, z) between two
the range indicated by Dance.[8]
almost coplanar aromatic rings which belong to the pair of
The coordination of the anion and acetonitrile group can molecules held together by the triflate bridge is also present
be considered as the first stage of the supramolecular or- in the structure. The local mirror symmetry would impose
ganization of the [Ag(LOH)2]ϩ unit; the analysis of the as- a much shorter contact between the two H atoms facing
˚
sembly of the [Ag(LOH)2(OTf)(CH3CN)] molecules follows each other (1.66 A), but this distance is relaxed by tilting
the steps outlined in the introduction.
the rings out of the common plane and introducing local
(i) The ϪOH donors are strongly linked to the triflate disorder.
acceptors of adjacent molecules by OH···O hydrogen bonds
(iii) A sixfold phenyl embrace[10] [6PE, C1···C1(v) ϭ
˚
˚
[O1···O3(ii) ϭ 2.849(5) A, O1ϪH···O3(ii) ϭ 171(5)°]: the 6.535(7) A, O1ϪC1···C1(v) ϭ 175.9(2)°] is formed between
[Ag(LOH)2(OTf)(CH3CN)] molecule uses its two ϪOH triaryl groups that are also involved in the CH3···π interac-
groups to hydrogen bond with the two triflate groups of a tions (Figure 4). The rotor conformation of the triaryl
pair of adjacent molecules related by a twofold screw axis; groups fits well in the 6PE and dictates the reciprocal orien-
concomitantly each triflate anion accepts two hydrogen tation of the rings also involved in the H···H contact. Re-
bonds from the ϪOH groups of two adjacent molecules, cently it has been shown by Bader and co-workers[11] that
generating the ϪOH···OϪSϪO···HOϪ tecton, with a short HϪH contacts between hydrogen atoms with similar
˚
OH···OH(vi) distance of 7.544(6) A. The overall arrange- charges can contribute up to 10 kcal/mol to the stabilization
ment consists of a double strand along the b axis (Figure 2). of the system where they occur. The assignment of stabiliz-
Eur. J. Inorg. Chem. 2004, 1985Ϫ1991
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1987

A. Bacchi, E. Bosetti, M. Carcelli, P. Pelagatti, D. Rogolino
SHORT COMMUNICATION
Figure 2. Association of the ϪOH···OϪSϪO···HOϪ tectons in double strands
Figure 3. Association of the hydrogen-bonded double strands in sheets, via CH3···π and CH3···CF3 interactions (dashed); the short H···H
˚
contacts are also dashed (2.36 A)
Figure 4. Sixfold phenyl embrace (6PE) involving molecules in the sheets shown in Figure 3; C···C contacts are dashed; the H···H short
interaction is also shown
ing character to a short HϪH interaction relies on the geometry [O2ϪAg···F3(iii)
analysis of the experimental electron-density topology; in (iii) ϭ 115.0(3)°].
ϭ
117.3(2)°, N2ϪAg···F3-
the absence of such evidence, it can be noted that the ob-
(iv) The main structural motif, the double strand, is based
served contact results from the balance of a local com- on the strongest and most directional tectons, the coordi-
pression required to optimize the 6PE geometry in the pres- nation bond AgϪO and the hydrogen bonds
ence of mirror symmetry, and a consequent rearrangement ϪOH···OϪSϪO···HOϪ involving the cation and the anion.
due to local overcrowding. The stabilization arising from The first useful observation to interpret and rationalize the
the 6PE geometry can equal up to 20 kcal molϪ1 [12]
and supramolecular arrangement of [Ag(LOH)2(OTf)(CH3CN)]
,
this could counterbalance the possible repulsion between is that the coordination of the anion to the [Ag(LOH)2]ϩ
symmetry-related aromatic rings, whilst the HϪH stabiliz- structural unit sets the concomitant presence of a pair of
ation could justify a slight distortion from the best 6PE ge- hydrogen-bond donors (LOH) and a pair of hydrogen-bond
ometry.
acceptors (ϪSO3Ϫ) on the complex neutral molecule. The
Finally, an examination of the metal environment shows molecule is divided into two halves, each one bearing a
that a long Ag···F3(iii) [3.542(6) A] contact completes the ϪOH and a ϪSϪOϪ function and behaving as a self-comp-
˚
silver environment giving a distorted trigonal bipyramidal lementary moiety. Each half of the [Ag(LOH)2(OTf)] unit
1988
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Eur. J. Inorg. Chem. 2004, 1985Ϫ1991

The Structural Role of the Triflate Anion in a Non-Covalent Silver Polymer
SHORT COMMUNICATION
[ϪAg(OSO)(LOH)] thus presents the requirements for self-
The association of the double strands described above,
association, which may be triggered by an inversion center built by the coordination bond AgϪO and the hydrogen
or by some twofold rotation relating two adjacent molecules bonds ϪOH···OϪSϪO···HOϪ, is governed by the forma-
(see a in Scheme 4). Also the basic [Ag(LOH)2]ϩ cation, tion of a 6PE tecton, which holds the strands together in
found in [Ag(LOH)2]BF4 and [Ag(LOH)2]PF6, bears two sheets. The sheets are also held together by the solvent,
ϪOH groups, both potential hydrogen bond donors and which adopts a structuring role, through the coordination
acceptors, but in that case the self-association could be dis- bond AgϪN and the short CH3···π and CH3···CF3 interac-
favored for two reasons: cation···cation repulsion, and the tions .
relatively poor accepting nature of alcoholic ϪOHs. We can
Finally, the sheets interact using the Ag···F tecton,
consider the dimeric system defined by the association of involving the anion. To investigate the role of the anion
two centrosymmetric [ϪAg(OSO)(LOH)] moieties as the and of the solvent in the crystal organization of
basic tecton for building the structural motif based on hy- [Ag(LOH)2(OTf)(CH3CN)], the local environment of the
drogen bonds. The association of the tectons in the double triflate anion was examined, see Figure 5. It appears that
strands of collinear complexes (see b in Scheme 4) is gov- the combination of the SϪO···HOϪ, the π···CH3, and the
erned by the nature of the anion: since the triflate fuses two CH3···CF3 individual tectons gives rise to a tetrafunctional
ϪSϪOϪ acceptors together, in the cis position relative to cyclic pattern that is very similar to the one already ob-
the metal, the complex must present a syn configuration of served in the related complexes [Ag(LOH)2]BF4 and [Ag-
the CϪOH vectors (χ ϭ 0°, Table 1) in order to pair all (LOH)2]PF6 (Scheme 5).[6] In these complexes there are two
the donors and all the acceptors in the self-complementary basic
independent
supramolecular
tectons
(the
structure. Different motifs could be engineered by choosing OH···FϪXϪF···HO pattern and the cyclic pattern involv-
a single hydrogen-bond acceptor X (formation of dimers, ing Ag···F, Ag···π and ϪOH···F interactions around the me-
with unsaturated terminal ϪOH groups) or a pair of single tal), which concur in creating two packing motifs: a chain
hydrogen-bond acceptors as trans ligands (formation of motif, generated by hydrogen bonds around the anions
chains with anti configuration of the complex, χ ϭ 180°) [···FϪXϪF···HOʝAgʝOH···FϪXϪF···]n, and a layer mo-
(see c in Scheme 4). Both cases have been studied for Pd tif, generated by the repetition of the Ag···F···HOϪC-π cy-
complexes.[13]
cle around the metal centers.
Figure 5. Structural role of the coordinated triflate anion; two mir-
ror-related tetrafunctional cyclic patterns are organized by combin-
ing the SϪO···HOϪ, the π···CH3 and the CH3···CF3 individual tec-
tons
In the present case, the methyl group of the acetonitrile
plays the structural function of the Ag atoms in the above
complexes, by bridging a triarylcarbinol group and the re-
lated hydrogen-bonded anion (Scheme 6). A pair of tetra-
functional cyclic patterns surround the anion in a mirror
symmetry linking five molecules together: one covalently
coordinated to the anion, two coordinated through hydro-
gen bonds, one through CF3···CH3 interactions, and one
through a CF3···Ag long contact. The long axes of the five
Ag(pyridine)2 systems are approximately parallel.
Scheme 4
Eur. J. Inorg. Chem. 2004, 1985Ϫ1991
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1989

A. Bacchi, E. Bosetti, M. Carcelli, P. Pelagatti, D. Rogolino
SHORT COMMUNICATION
double strands of collinear complexes in the syn configura-
tion: this results in a non-covalent supramolecular poly-
mer.[14] The solvent assists in the stabilization of the associ-
ation of the strands in sheets. The most striking feature of
the solid-state arrangement of [Ag(LOH)2(OTf)(CH3CN)]
is the plasticity of the molecule in response to the structural
function of the anion, which allows for the tuning of both
the coordination geometry and the configuration of the ter-
minal ϪOH groups in order to achieve the best self-comp-
lementary shape, thus giving the multitude of diverse inter-
actions highlighted in the course of the analysis.
Experimental Section
Synthesis: A solution of LOH (62 mg, 0.237 mmol) in THF (40
mL) was added to a solution of Ag(CF3SO3) (61 mg, 0.237 mmol)
in CH3CN (10 mL). The solution was stirred for 3 hours; diethyl
ether was added until a white precipitate formed. The mixture was
filtered and the precipitate was washed with diethyl ether. Yield
72%, m.p. Ͼ 123 °C (dec.). Colorless crystals suitable for X-ray
analysis were obtained by cooling mother liquors. C39H33Ag
F3N3O5S (820.372): calcd. C 57.09, H 4.02, N 5.12, S 3.90; found
1
C 56.61, H 4.11, N 5.55, S 3.94. H NMR (300 MHz, CDCl3, 25
3
°C): δϭ 8.57 (d, JH,H ϭ 6 Hz, 4 H, C(4)ϪH ϩ C(5)ϪH), 7.57 (d,
3JH,H ϭ 6 (Hz), 4 H, C(3)ϪH ϩ C(6)ϪH), 7.33Ϫ7.23 (m, 20 H,
Ar), 3.09 (br., 2 H, ϪOH), 2.00 (s, 3 H, CH3CN). IR [KBr (cmϪ1)]:
ν(OH): 3458 (m), ν(CN): 2255 (m), ν(SO): 1267 (m).
Scheme 5
˚
Crystallographic Analysis: Mo-Kα radiation (λ ϭ 0.71073 A), T ϭ
293 K (SMART AXS 1000 CCD diffractometer). Lorentz and pol-
arization corrections were applied.[15] Structure solved by direct
[16]
methods using SIR97
and refined by full-matrix least-squares
on all F2 using SHELXL-97,[17] implemented in the WingX pack-
age.[18] Hydrogen atoms located on Fourier difference maps and
refined isotropically except for the disordered parts, where they
have been introduced in idealized positions. Anisotropic displace-
ment parameters refined for all non-hydrogen atoms. The phenyl
group C13ϪC18 is disordered over two equally populated orien-
tations, in order to release steric overcrowding due to a crystallo-
graphic mirror plane passing close to C17. The removal of the mir-
ror plane and the modeling of the structure in the corresponding
P21 space group did not result in a unique conformation of the
ring. Hydrogen bonds have been analyzed with SHELXL-97[17] and
PARST97.[19] Crystal data: C39H33AgF3N3O5S, 0.10 ϫ 0.08 ϫ
0.03 mm, monoclinic, space group P21/m, a ϭ 8.4826(7), b ϭ
3
˚
˚
21.475(2), c ϭ 10.5455(9) A, β ϭ 101.144(2)°, V ϭ 1884.8(3) A ,
ρ ϭ 1.446 Mg·mϪ3, 2369 unique reflections, 1958 observed [I Ͼ
2σ(I)], 318 parameters, R1 ϭ 0.0355, wR2 ϭ 0.0933 [on I Ͼ 2σ(I)]
and R1 ϭ 0.0453, wR2 ϭ 0.0978 (on all data). For the analysis of
the organization of supramolecular tectons in the observed struc-
tures and for comparison with literature data, extended use has
been made of the software of the Cambridge Structural Database
(CSD).[20] The van der Waals radii used for assigning threshold
Scheme 6
˚
values to intermolecular contacts are (A): Ag 1.72, C 1.70, F 1.47,
Conclusions
H 1.20, N 1.55, O 1.52, S 1.80 (taken from CSD reference values).
CCDC-226532 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ44-1223-336-033; E-mail:
In [Ag(LOH)2(OTf)(CH3CN)], the structural role of the
anion is expressed through the coordination to the metal,
with the concomitant presence of the acetonitrile molecule.
We have uncoupled the function of the two LOH ligands
by observing that the anion triggers the formation of the deposit@ccdc.cam.ac.uk].
1990  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2004, 1985Ϫ1991

The Structural Role of the Triflate Anion in a Non-Covalent Silver Polymer
SHORT COMMUNICATION
[9]
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