Synthesis and structure of silver amino-arenesulfonates

Article abstract of DOI:10.1002/ejic.201101119

Treatment of a variety of zwitterionic amino-arenesulfonic acids with silver oxide has resulted in the synthesis of seven new Ag^I amino-arenesulfonates [Ag(O₃SR)]_∞ [R = o-aminobenzyl (oAB) (1), m-aminobenzyl (mAB) (2), 6-a

Full text of DOI:10.1002/ejic.201101119

FULL PAPER
DOI: 10.1002/ejic.201101119
Synthesis and Structure of Silver Amino-Arenesulfonates
Madleen Busse,[a] Philip C. Andrews,*[a] and Peter C. Junk[a]
Keywords: Silver / Arenesulfonates / Zwitterions / Coordination polymers
Treatment of a variety of zwitterionic amino-arenesulfonic
acids with silver oxide has resulted in the synthesis of seven
new AgI amino-arenesulfonates [Ag(O3SR)]ϱ [R = o-amino-
benzyl (oAB) (1), m-aminobenzyl (mAB) (2), 6-amino-3-
methoxybenzyl (6A3MB) (3), o-aminonaphthyl (oAN) (4), 5-
aminonaphthyl (5AN) (5), 4-amino-3-hydroxynaphthyl
(4A3HN) (6) and 5-isoquinolinyl (I) (7)]. This has allowed an
exploration of their coordination chemistry, whereby we ex-
amine the impact of structural diversity in the anions: the
position of the amino functionality on the arene moiety, in-
clusion of the N within a heterocycle and an increase in ring
size from phenyl to naphthyl. The solid-state structures of 1,
2 and two forms of 4, one with a coordinated water molecule,
have been determined by X-ray diffraction and are all poly-
meric. Analytical data is provided for two of the structurally
known complexes: known silver p-aminobenzenesulfonate 8
[Ag(O3SBAp)]ϱ and AgI 2-pyridinesulfonate [Ag(O3SP)]ϱ (9).
The composition of all nine complexes has been confirmed
through NMR spectroscopy, MS-ES+, FTIR and elemental
analysis.
Surprising is the fact that the majority of these applica-
tions have been developed only recently. Until around the
beginning of this century, the coordination chemistry of sulf-
onates was not well investigated or understood, the change
being marked by a series of papers by Côté and Shimizu et
al.,[2a,2b,2d–2f,6] Cai et al.[7] and others,[8] by investigating
metal sulfonates as a family of layered solids. The former
lack of activity most likely derives from our understanding
that the monoanionic sulfonate group is generally a weaker
coordinating ligand than other acidato anions such as car-
bonates or phosphonates,[6e–6g,9] often rendering the sulf-
onate ligand incapable of forming functional extended
solids. However, ligands that allow flexibility in their bind-
ing modes to metal centres have become more sought after,
and the number of coordination solids that incorporate
them in a variety of bonding modes and motifs has contin-
ued to increase over the past few years.[7a,10]
Systematic studies of AgI arenesulfonates have previously
been undertaken by Côté and Shimizu et al.,[2b] and more
recently by Zhu and Gao et al.[11] The former study charts
the influence of an increase in the size of the ring system
on observed structural outcomes, whereas in the latter, o-
hydroxy arenesulfonic acids, which contain one or more –
SO3H groups positioned at various points on a single
phenyl ring, are used to provide a diverse range of supra-
molecular frameworks.
Introduction
Interest in the medical and biological applications of sil-
ver metal and AgI complexes has grown substantially over
the past decade.[1] Today they are present as antimicrobial
agents in materials as diverse as topical creams for the treat-
ment of burns (e.g., AgI sulfadiazine) and in immobilized
polymer–silver membranes, which are now employed in a
wide range of infection-resistant biomedical devices, coated
medical instruments, wound dressings and in food-pro-
cessing equipment.[1]
The incorporation of silver nanoparticles into polymeric
membranes that contain sulfonated surfaces [e.g., sulf-
onated polyethersulfone (SPES)],[1c] polyvinyl sulfonate
(PVS),[1h] styrene sulfonate polymers[1g] and even naturally
available polysaccharides[1f] has proven to provide bacterici-
dal properties against a range of different bacteria, includ-
ing Staphylococcus aureus,[1c] Staphylococcus albus,[1c]
Staphylococcus epidermidis,[1h] Escherichia coli[1c] and Pseu-
domonas aeruginosa.[1d]
Beyond polymers, AgI sulfonate complexes themselves
have demonstrated potential application in selective and re-
versible guest inclusion,[2] especially when the metal–or-
ganic complexes incorporate neutral N-containing second-
ary ligands,[2g,2h,2k,3] whereas arenesulfonates have found
commercial application in the cosmetics industry as hair
dying agents[4] and in the laser and thermal printing indus-
try.[5]
Our current investigations represent the first systematic
study of the coordination chemistry of AgI amino-arene-
sulfonates. In choosing the range of amino-arenesulfonic
acids, four key structural factors were considered impor-
tant: (i) the position of the amino group on the arene moi-
ety would be varied from ortho to meta to para; (ii) hetero-
cyclic amines would be studied to increase structural diver-
[a] School of Chemistry, Monash University,
Melbourne, 3800 VIC, Australia
Fax: +61-3-9905-4597
E-mail: phil.andrews@monash.edu
Eur. J. Inorg. Chem. 2012, 1061–1071
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1061

M. Busse, P. C. Andrews, P. C. Junk
FULL PAPER
sity and to act as comparators with the exocyclic amines;
Possible coordination modes of the o-aminobenzenesulf-
(iii) the acids would be monoprotic zwitterions; and (iv) onate ligand involving the amino functionality are shown
ring size would be varied from phenyl to naphthyl. in Scheme 2 (only one type or a combination of these dis-
From this study we now report the synthesis and charac- played). The solid-state structures of complexes 1, 2, 4a and
terization of seven new AgI amino-arenesulfonates 4b have been determined by single-crystal X-ray diffraction,
[Ag(O3SR)]ϱ [R = o-aminobenzyl (oAB) (1), m-amino- and we provide further analytical data for the known silver
benzyl (mAB) (2), 6-amino-3-methoxybenzyl (6A3MB) (3), p-aminobenzenesulfonate[12] [Ag(O3SBAp)]ϱ 8 and AgI 2-
o-aminonaphthyl (oAN) (4), 5-aminonaphthyl (5AN) (5), 4- pyridinesulfonate[2i] [Ag(O3SP)]ϱ 9, since only structural in-
amino-3-hydroxynaphthyl (4A3HN) (6) and 5-isoquinolinyl formation has been reported thus far.
(I) (7)]. The acids are shown in Scheme 1.
Results and Discussion
Synthesis
Target compounds 1–9 were all synthesized from the ap-
propriate sulfonic acid and freshly prepared Ag2O[13] in
water at 90 °C by using the stoichiometric ratio of 2:1
(Scheme 3). Crystalline material suitable for single-crystal
X-ray diffraction studies was obtained through very slow
cooling of the homogeneous solution in a water bath to
room temperature for complexes 1, 2 and 4a, and for 4b
through recrystallization in a small amount of ethanol. All
1
the AgI complexes 1–9 were characterized through H and
13C NMR spectroscopy, FTIR and MS-ES+. Elemental
analysis and melting-point determination were also per-
formed.
Scheme 3. General reaction scheme of the synthesis of [Ag-
(O3SR)]ϱ [R = o-aminobenzyl (oAB) (1), m-aminobenzyl (mAB)
(2), 6-amino-3-methoxybenzyl (6A3MB) (3), o-aminonaphthyl
(oAN) (4), 5-aminonaphthyl (5AN) (5), 4-amino-3-hydroxy-
naphthyl (4A3HN) (6), 5-isoquinolinyl (I) (7), p-aminobenzyl
(pAB) (8) and 2-pyridyl (P) (9)].
X-ray Crystallographic Studies
[Ag(O3SBAo)]ϱ (1)
Compound 1 is represented by a 1D chain growing along
the crystallographic c axis (Figure 1). A summary of bond
lengths and angles is given in Table 1. In each chain only
one type of AgI centre is present and has a pseudo-tetrahe-
dral coordination geometry composed of two sulfonate oxy-
gen atoms, the nitrogen atom and two aromatic carbon
Scheme 1. Structures of the aminosulfonic acid ligands applied in
the synthesis of the AgI amino-arenesulfonates. X-ray structures
were obtained for those structures labelled with asterisks (*).
Scheme 2. Possible coordination modes shown for the o-aminobenzenesulfonate ligand in the solid-state involving the amino group in
bonding to the metal ion.
1062
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1061–1071

Synthesis and Structure of Silver Amino Arenesulfonates
atoms. This differs from the previously described 2-pyr- by linking four metal centres.[2i] Another key difference is
idinesulfonate analogue 9,[2i] in which the polymeric struc- the η2 interaction of the Ph ring with the Ag centre, which
ture forms a 2D network with one type of silver centre in an is apparent in 1 but not in 9.
asymmetrical trigonal-bipyramidal coordination geometry.
In contrast to 9, compound 1 possesses a µ2 [κ2-
The trigonal basis of the trigonal bipyramid is composed O(1),O(2)] coordination mode for the sulfonate group
of two sulfonate oxygen atoms in a µ4 [µ2O(1) and µ2O(3)] [Ag(1)–O(1), 2.496(3) Å; Ag(1)–O(2Ј), 2.335(3) Å (Ј = x,
bridging mode; the apices are occupied by one sulfonate –1/2 – y, z – 1/2)] and a κN bridge for the NH2 group
oxygen atom and the pyridyl nitrogen atom. Therefore, the [Ag(1)–N(1), 2.321(4) Å]. Thus, one o-aminobenzenesulfo-
2-pyridinesulfonate ligand stabilizes the molecular scaffold nate ligand is capable of connecting to three AgI centres in
an overall µ2:η3 coordination mode. No bridging sulfonate
oxygen atoms are observed in 1 and therefore no extended
network is formed. As might be expected with the amino
group in the ortho position, the AgI centre is chelated by
one sulfonate oxygen atom and the nitrogen atom to form
a boat-shaped six-membered ring. The arene moiety forms
a weak electrostatic interaction with the silver centre,
thereby establishing an η2 coordination mode from the 3,4-
positions of the ring [Ag(1)–C(3Ј), 2.521(4) Å; Ag(1)–C(4Ј),
2.502(4) Å (Ј = x, –1/2 – y, 1/2 – z)]. The interaction places
the phenyl ring perpendicular to the AgI centre [Ag(1)–
C(1)–C(4), 90.0(7)°] as the sulfur atom of the sulfonate
group holds on to its almost perfect tetrahedral geometry.
The packing of the 1D chains results in a 3D network in
which the individual 1D chains are connected through hy-
drogen-bonding interactions along the crystallographic a
Figure 1. Structure of [Ag(O3SBAo)]ϱ (1). View of an individual
axis (Figure 2), whereas π-stacking (face-to-face) interac-
1D polymeric chain growing along the crystallographic c axis show-
tions are observed along the crystallographic b axis. The 2-
ing the connectivity modes observed of the amino-arenesulfonate
ligand to the AgI centre. Hydrogen atoms are omitted for clarity.
Ellipsoids are shown at 50% probability.
pyridinesulfonate analogue 9 shows a perpendicular ar-
rangement of the phenyl rings along the crystallographic c
Table 1. Selected bond lengths [Å] and angles [°] of compounds 1, 2, 4a and 4b. Symmetry operators: 1 (Ј = x, –y – 1/2, z – 1/2); 2 (Ј =
–x + 1/2 – y, z + 1/2, ЈЈ = x + 1/2, –y + 1/2, –z); 3 (Ј = –x, y + 1/2, –z); 4 (Ј = –x, –y, –z, ЈЈ = x + 1/2, –y + 1/2, z – 1/2).
1
Ag(1)–N(1)
Ag(1)–O(2Ј)
Ag(1)–O(1)
Ag(1)–C(4Ј)
Ag(1)–C(3Ј)
2.324(3)
2.336(2)
2.497(3)
2.501(3)
2.522(3)
S(1)–O(3) 1.456(2)
S(1)–O(2) 1.457(2)
S(1)–O(1) 1.459(2)
N(1)–C(2) 1.416(4)
N(1)–Ag(1)–O(2Ј)
N(1)–Ag(1)–O(1)
O(2Ј)–Ag(1)–O(1)
S(1)–O(2Ј)–Ag(1)
S(1)–O(1)–Ag(1)
122.65(10)
80.54(9)
93.54(9)
142.12(17)
121.71(13)
O(3)–S(1)–O(2) 113.22(15)
O(3)–S(1)–O(1) 112.27(14)
O(2)–S(1)–O(1) 112.70(16)
2
Ag(1)–N(1Ј)
Ag(1)–O(2)
Ag(1)–O(1ЈЈ)
Ag(1)–O(1)
2.2402(18)
2.2957(13)
2.3719(15)
2.5168(14)
S(1)–O(3) 1.4504(14)
S(1)–O(2) 1.4557(16)
S(1)–O(1) 1.4678(15)
N(1)–C(3) 1.417(2)
N(1Ј)–Ag(1)–O(2)
N(1Ј)–Ag(1)–O(1ЈЈ)
O(2)–Ag(1)–O(1ЈЈ)
N(1Ј)–Ag(1)–O(1)
O(2)–Ag(1)–O(1)
142.19(6)
126.21(6)
88.46(5)
93.31(6)
94.42(5)
O(3)–S(1)–O(2) 113.84(9)
O(3)–S(1)–O(1) 111.92(8)
O(2)–S(1)–O(1) 111.64(9)
Ag(1ЈЈ)–O(1)–Ag(1) 111.34(5)
4a
Ag(1)–N(1)
Ag(1)–O(1)
Ag(1)–O(4)
Ag(1)–C(6Ј)
Ag(1)–C(7Ј)
2.320(6)
2.385(6)
2.397(5)
2.485(6)
2.464(7)
S(1)–O(3) 1.461(5)
S(1)–O(2) 1.472(5)
S(1)–O(1) 1.478(6)
S(2)–O(1) 1.462(5)
S(2)–O(3) 1.480(6)
C(2)–N(1) 1.397(8)
N(1)–Ag(1)–O(1)
N(1)–Ag(1)–O(4)
O(1)–Ag(1)–O(4)
N(1)–Ag(1)-C(7Ј)
S(1)–O(1)–Ag(1)
125.3(2)
86.9(2)
106.7(2)
108.6(2)
116.0(3)
O(3)–S(1)–O(2) 114.4(3)
O(3)–S(1)–O(1) 111.8(3)
O(2)–S(1)–O(1) 110.4(4)
4b
Ag(1)–N(1Ј)
Ag(1)–O(2Ј)
Ag(1)–O(1)
Ag(1)–C(6ЈЈ)
Ag(1)–C(7ЈЈ)
2.2829(16)
2.422(14)
2.4493(18)
2.5427(19)
2.5615(17)
S(1)–O(3) 1.4447(14)
S(1)–O(1) 1.4540(14)
S(1)–O(2) 1.4658(13)
N(1Ј)–Ag(1)–O(2Ј)
N(1Ј)–Ag(1)–O(1)
O(2Ј)–Ag(1)–O(1)
S(1)–O(1)–Ag(1)
S(1)–O(2Ј)–Ag(1)
127.95(5)
113.15(5)
101.31(4)
125.61(8)
109.90(7)
O(3)–S(1)–O(1) 113.35(9)
O(3)–S(1)–O(2) 111.09(8)
O(1)–S(1)–O(2) 110.97(8)
Eur. J. Inorg. Chem. 2012, 1061–1071
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1063

M. Busse, P. C. Andrews, P. C. Junk
FULL PAPER
axis to result in T-shaped C–H/π interactions between the
sheets (distance 3.698 Å). As the amino functionality is part
of the pyridyl ring, no hydrogen bonding is observed in 9.
Figure 3. Structure of [Ag(O3SBAm)]ϱ (2). A 3D network is ob-
tained for compound 2 as the amino group in the meta position on
the ring and one oxygen atom of the sulfonate group allow growth
of the network along the crystallographic c axis, whereas bridging
through sulfonate oxygen atoms allows growth along the crystallo-
graphic a and b axes. Hydrogen atoms of the asymmetric unit are
displayed. Ellipsoids are shown at 50% probability.
Figure 2. Hydrogen-bonding network of 1. Only hydrogen atoms
the bond to O(2) is the shortest at 2.2957(13) Å. The bridge
angle for O(1) is 111.35(6)°. As in 1 (and in 4b), the O(3)
atom is not involved in any bonding with the AgI centres.
Instead it bridges two hydrogen bonds [O(3ЈЈЈЈ)···H1–N(1),
2.34(3) Å (ЈЈЈЈ = –x, y + 1/2 –z + 1/2), O(3Ј)···H(2)–N(1),
2.08(3) Å (Ј = –x + 1/2, –y, z + 1/2)], which further enhances
the stability of the network along the crystallographic a
involved in hydrogen-bonding interactions are shown.
[Ag(O3SBAm)]ϱ (2)
Shifting the amino group to the meta position results in
complex 2, which forms a 3D network in the solid state.
The amino group and one oxygen atom of the sulfonate
group allow the network to grow along the crystallographic
c axis, whereas bridging through the second and third sulf-
onate oxygen atoms allows growth along the divergent crys-
tallographic a and b axes. Only one type of AgI centre is
present and again shows pseudo-tetrahedral geometry.
However, one AgI centre is connected to four individual m-
aminobenzenesulfonate ligands to exhibit an overall µ4:η4
coordination mode (Figure 3). The pyridyl complex [Ag(3-
pySO3)]ϱ, previously described by Mäkinen and Shimizu et
al.,[2d] also forms a 3D network that consists of AgI ribbons
growing along the crystallographic c axis. However, this
compound accommodates two types of AgI ions, analogous
to those previously observed in the AgI 2-pyridinesulfonate
analogue 9.[2i] In [Ag(3-pySO3)]ϱ only one metal centre is
bound to sulfonate oxygen atoms, whereas the other binds
through the third sulfonate oxygen atom and the pyridyl
nitrogen atom.
As might be expected for this family of compounds, the
amino group of 2 engages in a κN bridge to the AgI centre
[Ag(1)–N(1Ј), 2.241(2) Å (Ј = 1/2 – x, –y, 1/2 + z)] and
forms the shortest Ag–N bond of all the complexes 1, 4a
and 4b (see below). A summary of bond lengths and angles
is given in Table 1. The sulfonate group adopts a µ3:η3 coor-
dination mode [κ2O(1) and κO(2)]. The oxygen atom O(1)
bridges two AgI centres thereby showing two different Ag–
O bonds [O(1ЈЈ)–Ag(1), 2.3719(15) Å (ЈЈ = x + 1/2, 1/2 –
Figure 4. Display of the hydrogen bonds bridged by O(3) of the
sulfonate group, which further enhances the stability of the network
of 2 along the crystallographic a axis; the hydrogen bonds of one
repeating unit show the motif of an R-helix winding down the crys-
y, –z), O(1ЈЈЈ)–Ag(1), 2.5168(14) Å (ЈЈЈ = x,y,z)], whereas tallographic a axis.
1064
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1061–1071

Synthesis and Structure of Silver Amino Arenesulfonates
axis; the hydrogen bonds of one repeating unit show the tains the sulfonate moiety [Ag(1)–C(6ЈЈ), 2.464(7) Å; Ag(1)–
motif of an R helix winding down the crystallographic a C(7ЈЈ), 2.467(7) Å (ЈЈ = –x, 1/2 + y, –z)]. On account of this
axis (Figure 4). The phenyl group in 2 packs in a classical coordination environment, the ligand is locked into place as
herringbone motif (also seen in 4b below) that shows an the naphthyl moiety is perpendicular to the sulfonate group
array of nonclassical C–H/π-stacking interactions along the [S(1)–C(1)–C(9), 89.5(2)°] and the η2 coordination mode
two crystallographic axes defined by the face-to-edge con- from the 6,7-positions of the ring to the silver centre is fixed
tacts of the phenyl ring.
by a mean angle of 109.2(8)°. The coordination sphere of
the silver centre is completed by an auxiliary ligation to one
water molecule [Ag(1)–O(4), 2.397(5) Å] that points to the
left and right of the chain.
[Ag(O3SNAo)(H2O)]ϱ (4a)
It is known that AgI mono-sulfonates will generally form
anhydrous solids even when synthesized and isolated from
aqueous solutions.[2b] There are rare exceptions to this and
compound 4a is one. The crystal structure shows one water
molecule binding directly to the metal centre. This phenom-
enon was first observed in [Ag(H2O)0.5(1-naphthylenesulf-
[2b]
onate)]ϱ
and was ascribed to the increased length of the
naphthyl moiety. The increased intramolecular space cre-
ated by the naphthyl group also allows 4a to retain the
structural motif of the 1D chain, as adopted by the Ph ana-
logue 1. Bridging water molecules are thus incorporated
into the polymeric chain (Figure 5), thus saturating the co-
ordination environment of the AgI centre.
Figure 6. Hydrogen-bonding network of 4a. The two sulfonate oxy-
gen atoms that are not involved in the direct bonding to the metal
centre play a significant role in intermolecular hydrogen bonding
between the 1D chains; they are connected along the crystallo-
graphic a axis. An intramolecular hydrogen bond is observed for
O(3) as a secondary interaction seen within one chain.
Looking down the crystallographic a axis, a zigzag
pattern occurs similar to that observed in 1. The two indi-
vidual silver(I) chains are orientated exactly opposite to
each other with respect to the arene moiety and its func-
tional groups. The zigzag angle at the silver centre is
62.1(3)°. This facilitates a perfect alignment of the naphthyl
rings to allow T-shaped C–H/π interactions (face-to-edge)
with a distance of 3.581 Å. These interactions are also pres-
ent between individual chains, which results in an overall
Figure 5. Structure of [Ag(O3SNAo)(H2O)]ϱ (4a). View of an indi-
vidual 1D polymeric chain growing along the crystallographic b
axis showing the connectivity modes observed of the amino-arene-
sulfonate ligand to the unique AgI centre. Hydrogen atoms are
omitted for clarity. Ellipsoids are shown at 50% probability.
As in 1, the 1D chain in 4a grows along the crystallo- classical herringbone motif along the crystallographic c
graphic b axis. In turn, only one unique AgI centre is again axis, as reported for simple aromatic hydrocarbons,[14]
present and once more displays pseudo-tetrahedral coordi- naphthalene itself[12e] and its AgI arenesulfonate ana-
nation geometry. However, significant differences in the logue.[2b] The two sulfonate oxygen atoms that are not in-
connectivity are seen due to the much more expanded struc- volved in bonding to the metal centre play a significant role
ture (Figure 3). A summary of the bond lengths and angles in intermolecular hydrogen bonding between the 1D chains;
is given in Table 1. Here only O(1) of the sulfonate group two originate from the water molecule [O(1ЈЈ)···H(9)–O(4),
[Ag(1)–O(1), 2.383(6) Å] is involved in bonding to the metal 2.040(8) Å, O(2ЈЈ)···H(10)–O(4), 2.390(15) Å (ЈЈ = –x, 1/2 +
centre. The sulfonate and amino groups show no chelation y, –z)] and two from the amino functionality [O(2ЈЈ)···H(1)–
to any AgI centre. Instead the nitrogen atom bridges to a N(1), 2.55 Å, O(3ЈЈ)···H(2)–N(1), 2.36 Å (ЈЈ = –x, 1/2 + y,
second AgI centre [Ag(1)–N(1Ј), 2.320(6) (Ј = x, y, z)]. The –z)]; and connect them along the crystallographic a axis
AgI centre is again involved in π bonding to the arene moi- (Figure 6). Another intramolecular hydrogen bond is ob-
ety (Figure 6), but here the interaction is established with served for O(3) [O(3)···H(1)–N(1), 1.88 Å] as a secondary
the more distant phenyl ring rather than that which con- interaction within one chain (Figure 6).
Eur. J. Inorg. Chem. 2012, 1061–1071
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1065

M. Busse, P. C. Andrews, P. C. Junk
FULL PAPER
{[Ag(O3SNAo)]·H2O}ϱ (4b)
2.450(2) Å; and Ag(1)–O(2Ј), 2.4230(2) Å (Ј = –x, –y, –z)].
To maintain the pseudo-tetrahedral geometry around the
AgI centre, the arene moiety coordinates in an η2 mode
from the 6,7-positions of the ring [Ag(1)–C6ЈЈ, 2.5620(2) Å;
Ag(1)–C7ЈЈ, 2.5620(2) Å (ЈЈ = 1/2 + x, 1/2 – y, 1/2 + z)].
Again O(3) of the sulfonate group is not involved in bond-
ing to the AgI centre (Figure 7).
A summary of bond lengths and angles for 4b is given
in Table 1. Five hydrogen bonds are observed within the
structure (Figure 8): two derived from the amino group
[O(1)···H2–N(1), 1.990(2) Å, O4···H1–N(1), 2.250(2) Å] and
three from the water molecule that are present in the lattice
[O(3)···H9–O4, 2.2400(2) Å, O(3Ј)···H9–O4, 2.4500(2) Å
(Ј = –x, y, –z + 1/2) and O(2Ј)Ј···H10–O4, 1.9900(2) Å (ЈЈ =
x, –y, z – 1/2)]. Compound 4b is assigned as an anhydrous
AgI amino-arenesulfonate as the coordination geometry
around the AgI centre is exclusively made up of the ligand
and does not include the water molecule.
In attempting to generate the anhydrous analogue of 4a,
crystals of 4a were dissolved in ethanol and recrystallized.
The result was complex 4b, which retains a water molecule
in the crystal lattice but not directly bound to the AgI cen-
tre. The absence of water bridging to the silver centre allows
the formation of a 2D network that grows along the crystal-
lographic b axis. The overall pseudo-tetrahedral geometry
of the unique metal centre similar to that seen in 4a (and
in 1) is maintained. As in compound 1, two sulfonate oxy-
gen atoms coordinate to the AgI centre along with the nitro-
gen atom and two aromatic carbon atoms. In contrast to 1,
however, the formation of a 2D network and the accommo-
dation of the naphthyl moiety do not allow the chelation of
the ligand to the metal centre. Therefore, in 4b an overall
coordination mode of µ3:η3 to three independent AgI
centres is present [Ag(1)–N(1Ј), 2.2830(2) Å; Ag(1)–O(1),
Characterization
Complexes 1–9 and the starting acids were all studied by
1
NMR spectroscopy in D2O and/or [D6]DMSO. In the H
NMR spectra the acids show the acidic proton as a broad
singlet with chemical shift values in the range δ = 7–9 ppm.
Upon deprotonation and complexation with AgI, this signal
disappears thereby confirming formation of the ligand and
the corresponding silver compounds. In comparison with
the free acids, upon complexation the 13C NMR spectra
show low-frequency shifts for the resonance that corre-
sponds to the quaternary carbon C-(SO3Ag) by between
Table 2. Observed coordination modes for AgI to the sulfonate
group and the assignment of the corresponding absorption bands.
Figure 7. Structure of {[Ag(O3SNAo)]·(H2O)}ϱ (4b). Connectivity
of compound 4b is shown with µ3:η3 coordination mode to three
independent AgI centres. Hydrogen atoms of the asymmetric unit
are shown. Ellipsoids are shown at 50% probability.
ν(NH )[a]
ν(SO )[a]
CM[b] CS[c]
˜
˜
2
3
oABSO3H
1
mABSO3H
2
6A3MBSO3H 3391
3
oANBSO3H
4a
3418
1228, 1204, 1027
3320, 3257 1204, 1174, 1013
3437 1208, 1101, 1026
3362, 3246 1210, 1147, 1108, 1027
1260, 1187, 1024
3336, 3070 1253, 1186, 1134, 1023
3470 1242, 1182, 1045
µ2:η3
µ4:η4
x
x
3433, 3342 1193, 1050
3412, 3341 1158, 1029
µ2:η2
µ3:η3
x
x
4b
5ANSO3H
3421
1226, 1170, 1057
5
3401, 3348 1167, 1027
3H4ASO3H
3239
1218, 1169, 1048
6
3159, 3078 1197, 1157, 1042
ISO3H
7
pABSO3H
8
3429
3437, 3351 1210, 1175, 1056
3418 1245, 1156, 1033
3319, 3266 1249, 1186, 1153, 1123
1215, 1198, 1052
µ4:η4
µ5:η5
x[d]
x[e]
PSO3H
9
–
–
1269, 1148, 1039
1207, 1165, 1146, 1019
[a] FTIR absorption bands are taken from the Nujol spectra [cm–1].
[b] CM = coordination mode. CM assigned in red were confirmed
through X-ray crystallography. [c] CS = crystal structure. Overall
CM was confirmed through X-ray crystallography. [d] Crystal
structure is known in the literature of compound [Ag(2-
pySO3)]ϱ.[2i] [e] Crystal structure is known in the literature of com-
pound [Ag(O3SBAp)]ϱ.[12a–12d]
Figure 8. Hydrogen-bonding network of 4b. Only hydrogen atoms
involved in hydrogen-bonding interactions are shown.
1066
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1061–1071

Synthesis and Structure of Silver Amino Arenesulfonates
3 and 5 ppm. Full details of the chemical shifts and their dral geometry. This phenomenon of having a unique AgI
assignments for 1–9 are given in the Experimental Section. centre is in contrast to the reported pyridyl analogues,
FTIR spectra visualize the different coordination modes which consist of two geometrically different AgI centres.
of the silver metal to the sulfonic acid group by showing Despite being synthesized in water, anhydrous compounds
the appropriate number of absorption bands. A batho- were obtained for all compounds 1–9. An exception is the
chromic shift for the amino absorption band is ascribed to o-aminonaphthalenesulfonate ligand 4a, which results in a
the coordination of the amino functionality to the AgI cen- hydrated solid structure with one water molecule bound di-
tre. The sulfonate group shows a range of absorption bands rectly to the Ag centre. Recrystallization from ethanol
in the region 1200–1000 cm–1 according to the coordination yielded the anhydrous compound.
mode this functional group displays within the solid-state
We are currently exploring the antimicrobial properties
structure. The coordination modes for 1, 2, 4a, 4b, 8 and 9 of these compounds for use in medical applications (see In-
have been established through crystallography and as such troduction) and assessing their potential as precursors to
their coordination mode is known. Table 2 summarizes the new metal sulfonates through metathesis, especially when
main features observed in FTIR spectroscopy and the ob- the zwitterionic nature of the aminosulfonate inhibits direct
served bonding modes of the sulfonato ligands. However, complex formation.
too little data currently exists to allow the binding and co-
ordination of the other complexes to be predicted based on
the IR spectroscopic data alone.
Mass spectrometry provided unambiguous evidence for
General Considerations: All sulfonic acids were purchased from
silver complexes 1–9 to be arranged as polymeric structures.
Aldrich Chemical Co. Ag2O was freshly synthesized according to
Experimental Section
In the case of the p-aminobenzenesulfonate, two quartets
(1/3/3/1) at 665/667/669/671 [Ag3L2]+ and 743/745/747/749
[Ag3L2(DMSO)]+ and a quintet (1/4/6/4/1) at 944/946/948/
950/952 [Ag4L3]+ were observed underlining the polymeric
nature of the silver compound 8. A summary of the com-
mon ions detected for all the structures can be found in
Table 3.
Tanabe and Peters.[13] Infrared spectra were obtained with a Per-
kin–Elmer 1600 FTIR spectrometer. NMR spectra were obtained
with Bruker AV300 or AV400 spectrometers with chemical shifts
referenced to [D6]DMSO or D2O. Electrospray ionization mass
spectrometry (ESI-MS) was performed with a Micromass Platform
electrospray mass spectrometer. Elemental analysis (EA) was per-
formed by The Campbell Microanalytical Laboratory, Department
of Chemistry, University of Otago, New Zealand. Melting points
are uncalibrated and were determined with a Bibby Stuart Scien-
tific melting-point apparatus SMP3.
Table 3. Summary of common ions detected in mass spectra for
compounds 1–9.
L–
[AgL + Na]+ [AgL(s) + Na]+ [Ag2L]+
[Ag2L(s)]+
Synthesis, General Procedure: The individual sulfonic acid (2 mmol,
2 equiv.) was dissolved in water ( 50 mL) and the temperature was
set to 90 °C. Fresh Ag2O (1 mmol, 1 equiv.) was added to this solu-
tion, and the reaction mixture was stirred for 2 h. The solution was
filtered hot and the filtrate was kept in a water bath at 50 °C over-
night. The filtrate was allowed to cool to room temperature very
slowly to yield the desired product either as crystalline material (1,
2, 4a, 4b, 8 and 9) or as an amorphous powder (3, 5–7).
1
2
3
oABSO3
mABSO3 302/304
6A3MBSO3332/334
386/388/390 464/466/468[b]
386/388/390 464/466/468[b]
4a oANSO3
436/438/440 520/522/524[c]
436/438/440
5
6
7
8
5ANSO3
3H4ANSO3368/370
ISO3
470/472/474[a]
356/358[a]
pABSO3
464/466/468[b]
542/544/546[b]
[Ag(O3SBAo)]ϱ (1): The general procedure was followed using o-
aminobenzenesulfonic acid to yield pink crystalline needles
(269 mg, 96%) suitable for X-ray crystallography; m.p. Ͼ 250 °C
*
9
PSO3
372/374/376 456/458/460[c]
[a] Solvent H2O. [b] Solvent DMSO or * (DMSO)2. [c] Solvent
dichloromethane.
1
(decomp.). H NMR (300 MHz, [D6]DMSO, 30 °C): δ = 7.43 (dd,
3J = 1.6, 7.7 Hz, 1 H, H6), 7.02 (ddd, 3J = 3.0, 3.0, 6.0 Hz, 1 H,
3
3
H4), 6.66 (dd, J = 1.6, 7.7 Hz, 1 H, H3), 6.51 (ddd, J = 3.0, 3.0,
6.0 Hz, 1 H, H5) ppm. 13C NMR (75 MHz, [D6]DMSO, 30 °C): δ
= 144.69 (C1), 130.88 (C2), 129.72 (C6), 127.21 (C4), 116.04 (C3),
Conclusion
115.43 (C5) ppm. FTIR (KBr): ν = 3424 (m), 3370 (m), 1619 (s),
˜
1560 (s), 1482 (s), 1317 (m), 1231 (s), 1187 (s), 1117 (m), 1065 (w),
1023 (m), 1035 (m), 826 (w), 750 (s), 709 (s), 619 (s), 576 (m), 528
We have described the synthesis and characterization of
seven new AgI amino-arenesulfonates and a systematic
study on their coordination chemistry. Mass spectroscopic
data indicate the compounds to be polymeric in nature and
are supported by those complexes 1, 2, 4a and 4b that have
been confirmed by single-crystal X-ray diffraction. Struc-
tural changes in the position of the amino functionality on
the arene moiety from ortho to meta to para, the increase
in ring size from a phenyl to a naphthyl moiety and in-
clusion of the N atom in a heterocycle all impact directly
on the adopted structures. All presented structures have a
(m) cm–1. FTIR (Nujol): ν = 3320 (m), 3257 (m), 1599 (w), 1565
˜
(w), 1296 (w), 1204 (s), 1174 (s) 1160 (m), 1131 (m), 1074 (m), 1033
(m), 1013 (s), 947 (w), 827 (m), 778 (s), 703 (s) cm–1. ESI-MS+
(solvent: DMSO/MeOH): m/z (%) = 464/466/468 (5) {triplet (1/2/1
107Ag/107/109Ag/109Ag), [Ag2L(DMSO)]+}; 386/388/390 (5) {triplet
(1/2/1 107Ag/107/109Ag/109Ag), [Ag2L]+}; 263/265 (95) {doublet (1/1
107Ag/109Ag), [Ag(L–NH2)]+}; 185/187 (100) {doublet (1/1 107Ag/
109Ag), [Ag(DMSO)]+}. C6H6AgNO3S (280.046): calcd. C 25.73, H
2.16, N 5.00; found C 25.57, H 2.06, N 4.87.
[Ag(O3SBAm)]ϱ (2): m-Aminobenzenesulfonic acid was applied to
unique silver ion incorporated that displays pseudo-tetrahe- the general procedure to yield a dark purple amorphous powder
Eur. J. Inorg. Chem. 2012, 1061–1071
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1067

M. Busse, P. C. Andrews, P. C. Junk
FULL PAPER
(258 mg, 92%). Recrystallization of 50 mg in water resulted in crys-
talline plates (55%) suitable for X-ray crystallography; m.p.
Ͼ 270 °C (decomp.). 1H NMR (300 MHz, [D6]DMSO, 30 °C): δ =
7.03 (m, 1 H, H5), 6.99 (s, 1 H, H2), 6.91 (d, 3J = 9.0 Hz, 1 H, H6),
6.62 (m, 1 H, H4) ppm. 13C NMR (100 MHz, [D6]DMSO, 30 °C):
δ = 148.49 (C1), 146.47 (C3), 128.15 (C5), 115.47 (C4), 114.89 (C6),
C10H9AgNO3.5S (339.112): calcd. C 35.42, H 2.68, N 4.13; found
C 32.36, H 2.60, N 3.99.
{[Ag(O3SNAo)]·(H2O)0.5}ϱ (4b): Crystalline material of 4a (50 mg)
was dissolved in EtOH and left for crystallization. After one week,
pink needles were obtained [yield: 28 mg (56%)] that were suitable
for X-ray crystallography. The crystals were isolated and dried in
vacuo. Further analysis indicates the loss of the water molecule
present in the lattice; m.p. Ͼ 160 °C (decomp.). C10H8AgNO3S
(330.104): calcd. C 36.38, H 2.44, N 4.24; found C 37.57, H 2.98,
N 4.53.
112.82 (C2) ppm. FTIR (KBr): ν = 3432 (s), 1629 (m), 1600 (m),
˜
1482 (m), 1452 (m), 1384 (m), 1313 (w), 1270 (w), 1188 (s), 1110
(s), 1037 (s), 992 (m), 875 (w), 791 (m), 710 (s), 691 (m), 623 (s),
562 (m), 526 (m) cm–1. FTIR (Nujol): ν = 3362 (m), 3246 (w), 1599
˜
(m), 1314 (w), 1254 (m), 1210 (s), 1169 (m), 1147 (s), 1108 (s), 1027
(s), 982 (m), 881 (m), 785 (m), 709 (m), 685 (m), 613 (m) cm–1. ESI-
MS+ (solvent: DMSO/MeOH): m/z (%) = 464/466/468 (5) {triplet
(1/2/1 107Ag/107/109Ag/109Ag), [Ag2L(DMSO)]+}; 386/388/390 (5)
{triplet (1/2/1 107Ag/107/109Ag/109Ag), [Ag2L]+}; 313/315 (10)
{doublet (1/1 107Ag/109Ag), [Ag(L–NH2)(MeOH)(H2O)]+}; 302/304
(5) {doublet (1/1 107Ag/109Ag), [AgL + Na]+}; 263/265 (95)
{doublet (1/1 107Ag/109Ag), [Ag(L–NH2)]+}; 185/187 (100) {doublet
(1/1 107Ag/109Ag), [Ag(DMSO)]+}; 107/109 (30){doublet (1/1),
[Ag]+}. C6H6AgNO3S (280.046): calcd. C 25.73, H 2.16, N 5.00;
found C 25.80, H 2.14, N 5.22.
[Ag(O3SN5A)]ϱ (5): The general procedure was followed by using
5-amino-1-naphthalenesulfonic acid to yield a dark red amorphous
powder (293 mg, 89%); m.p. Ͼ 220 °C (decomp.). 1H NMR
3
(300 MHz, [D6]DMSO, 30 °C): δ = 8.86 (d, J = 6.0 Hz, 1 H, H9),
3
3
8.05 (d, J = 9.0 Hz, 1 H, H4), 7.95 (d, J = 9.0 Hz, 1 H, H2), 7.59
(d, 3J = 9.0 Hz, 1 H, H3), 7.55–7.52 (m, 2 H, H7 and H8) ppm. 13
C
NMR (100 MHz, [D6]DMSO, 30 °C): δ = 144.39 (C1), 129.73 (C6),
128.58 (C10), 127.46 (C9), 126.71 (C5), 125.66 (C3), 125.41 (C4),
125.25 (C8), 122.93 (C2), 119.71 (C7) ppm. FTIR (KBr): ν = 3469
˜
(s), 1654 (s), 1399 (m), 1384 (m), 1350 (w), 1322 (w), 1199 (s), 1035
(s), 785 (m), 755 (w), 646 (m), 581 (m) cm–1. FTIR (Nujol): ν =
˜
[Ag(O3SBM3A6)]ϱ (3): The general procedure was followed by
using 6-amino-3-methoxybenzenesulfonic acid to yield a dark pur-
ple amorphous powder (289 mg, 93%); m.p. Ͼ 150 °C (decomp.).
3427 (w), 1654 (m), 1167 (s), 1027 (s), 783 (m), 645 (w), 629 (w),
582 (w) cm–1. ESI-MS+ (solvent: DMSO/MeOH): m/z (%) = 436/
438/440 (5) {triplet (1/2/1 107Ag/107/109Ag/109Ag), [Ag2L]+}; 341/343
(60) {doublet (1/1 107Ag/109Ag), [Ag(DMSO)3]+}; 263/265 (60)
{doublet (1/1 107Ag/109Ag), [Ag(DMSO)2]+}; 217/219 (10) {doublet
(1/1 107Ag/109Ag), [Ag(DMSO)(MeOH)]+}; 185/187 (100) {doublet
(1/1 107Ag/109Ag), [Ag(DMSO)]+}. C10H12AgNO5S (366.134):
calcd. C 32.80, H 2.75, N 3.83; found C 32.36, H 2.72, N 3.83.
3
1H NMR (300 MHz, [D6]DMSO, 30 °C): δ = 7.28 (d, J = 6.0 Hz,
1 H, H3), 7.26 (s, 1 H, H6), 7.04 (dd, 3J = 3.0, 9.0 Hz, 1 H, H4), 3.79
(s, 3 H, –OCH3) ppm. 13C NMR (100 MHz, [D6]DMSO, 30 °C): δ
= 158.39 (C2), 141.78 (C5), 125.41 (C3), 120.08 (C1), 115.96 (C4),
112.21 (C6), 55.66 (C7) ppm. FTIR (KBr): ν = 3448 (s), 3079 (s),
˜
1608 (m), 1560 (m), 1508 (m), 1492 (s), 1411 (w), 1384 (w), 1330
(m), 1252 (s), 1236 (s), 1210 (s), 1197 (s), 1132 (s), 1093 (m), 1060
(s), 1022 (s), 886 (m), 829 (m), 696 (s), 670 (w), 638 (s), 627 (s), 560
[Ag(O3SN4A3H)]ϱ (6): 4-Amino-3-hydroxy-1-naphthalenesulfonic
acid was applied to the general procedure to yield a dark red
amorphous powder (276 mg, 80%); m.p. 176–180 °C. 1H NMR
(300 MHz, D2O, 30 °C): δ = 8.51–8.48 (m, 1 H, H9), 8.12–8.09 (m,
1 H, H6), 7.84 (s, 1 H, H2), 7.56–7.52 (m, 2 H, H7 and H8) ppm.
13C NMR [100 MHz, D2O (TMS), 30 °C]: δ = 140.34 (C3), 137.16
(C1), 130.24 (C4), 126.02 (C9), 125.97 (C10), 125.37 (C7), 124.82
(w), 527 (m) cm–1. FTIR (Nujol): ν = 3077 (m), 1634 (w), 1608
˜
(w), 1494 (s), 1413 (w), 1331 (w), 1253 (s), 1237 (s), 1211 (s), 1186
(s), 1134 (m), 1095 (w), 1061 (m), 1023 (s), 888 (m), 830 (m), 697
(s), 639 (m), 629 (m) cm–1. ESI-MS+: (solvent: DMSO/MeOH): m/z
(%) = 332/334 (10) {doublet (1/1 107Ag/109Ag), [AgL + Na]+}; 310/
312 (10) {doublet (1/1 107Ag/109Ag), [AgL + H]+}; 122/124 (25)
{doublet (1/1 107Ag/109Ag), [Ag2O + H]+}; 107/109 (100) {doublet
(1/1), [Ag]+}. C7H8AgNO4S (310.071): calcd. C 27.11, H 2.60, N
4.52; found C 27.27, H 2.81, N 5.21.
(C8), 124.17 (C5), 121.12 (C6), 118.90 (C2) ppm. FTIR (KBr): ν =
˜
3169 (s), 1637 (s), 1607 (m), 1577 (m), 1514 (m), 1441 (s), 1400 (s),
1352 (s), 1290 (m), 1221 (s), 1196 (s), 1159 (m), 1145 (m), 1105 (m),
1081 (m), 1043 (s), 983 (w), 970 (m), 877 (m), 781 (w), 759 (m),
725 (w), 656 (m), 640 (m), 593 (s), 545 (m), 514 (m) cm–1. FTIR
[Ag(O3SNAo)(H2O)0.5]ϱ (4a): The general procedure was carried
(Nujol): ν = 3156 (m), 1635 (m), 1601 (m), 1576 (m), 1515 (m),
˜
out with o-amino-1-naphthalenesulfonic acid to yield pale pink
crystalline needles (304 mg, 92%) suitable for X-ray crystallogra-
phy; m.p. Ͼ 140 °C (decomp.). 1H NMR (300 MHz, [D6]DMSO,
1351 (s), 1292 (m), 1197 (s), 1157 (s), 1145 (s), 1105 (m), 1042 (s),
969 (m), 946 (w), 878 (w), 760 (m), 676 (w), 657 (m), 640 (m), 594
(m) cm–1. ESI-MS+ (solvent: DMSO/MeOH): m/z (%) = 470/472/
474 (5) {triplet (1/2/1 107Ag/107/109Ag/109Ag), [Ag2L + H2O]+}; 368/
370 (10) {doublet (1/1 107Ag/109Ag), [AgL + Na]+}; 147/149 (100)
{doublet (1/1 107Ag/109Ag), [AgOH + Na]+}. AgC10H12O6NS
(382.131): calcd. C 31.43, H 3.17, N 3.67; found C 31.05, H 3.04,
N 3.82.
3
3
30 °C): δ = 8.95 (d, J = 6.0 Hz, 1 H, H9), 7.96 (d, J = 9.0 Hz, 1
H, H4), 7.88 (d, J = 9.0 Hz, 1 H, H6), 7.59–7.46 (m, 2 H, H7 and
3
H8), 7.29 (d, 3J = 9.0 Hz, 1 H, H3) ppm. 13C NMR (100 MHz, [D6]-
DMSO, 30 °C): δ = 143.16 (C1), 131.98 (C2), 129.83 (C4), 127.35
(C10), 126.77 (C6), 126.08 (C9), 125.41 (C5), 120.61 (C8), 120.31
(C7), 118.97 (C3) ppm. FTIR (KBr): ν = 3430 (s), 2959 (w), 2625
˜
(w) 1624 (s), 1559 (s), 1552 (s), 1518 (s), 1473 (m), 1427 (m), 1384 [Ag(O3SI)]ϱ (7): The general procedure was carried out with 5-iso-
(s), 1360 (w), 1332 (w), 1233 (m), 1200 (s), 1145 (m), 1050 (s), 990
quinolinesulfonic acid to yield a pale yellow amorphous powder
(m), 913 (w), 881 (w), 827 (w), 809 (s), 779 (m), 763 (w), 749 (w), (308 mg, 98%); m.p. Ͼ 220 °C (decomp.). 1H NMR (300 MHz,
676 (m), 655 (m), 623 (m), 559 (m), 513 (m) cm–1. FTIR (Nujol): [D6]DMSO, 30 °C): δ = 9.37 (s, 1 H, H6), 8.71 (d, J = 6.0 Hz, 1
3
3
3
ν = 3433 (w), 3342 (w), 1611 (m), 1597 (w), 1553 (m), 1503 (m),
˜
H, H4), 8.54 (d, J = 6.0 Hz, 1 H, H3), 8.21 (dd, J = 3.0, 9.0 Hz,
1351 (w), 1234 (w), 1193 (s), 1146 (m), 1050 (s), 991 (m), 905 (w), 1 H, H10), 8.16 (d, 3J = 9.0 Hz, 1 H, H8), 7.69 (dd, 3J = 3.0, 9.0 Hz,
828 (w), 810 (m), 782 (m), 764 (w), 676 (m), 657 (w), 623 (m) cm–1. 1 H, H9) ppm. 13C NMR (100 MHz, [D6]DMSO, 30 °C): δ =
ESI-MS+ (solvent: CH2Cl2): m/z (%) = 520/522/524 (5) {triplet
(1/2/1 107Ag/107/109Ag/109Ag), [Ag2L(CH2Cl2)]+}; 436/438/440 (5)
{triplet (1/2/1 107Ag/107/109Ag/109Ag), [Ag2L]+}; 275/277 (5)
{doublet (1/1), [Ag(CH2Cl2)2]+}; 191/193 (100) {doublet (1/1),
153.92 (C6), 143.17 (C10), 143.10 (C1), 131.88 (C2), 129.46 (C8),
129.18 (C3), 128.68 (C9), 126.97 (C7), 120.90 (C4) ppm. FTIR
(KBr): ν = 3435 (s), 3093 (w), 3070 (w), 3026 (w), 3008 (w), 1622
˜
(s), 1558 (s), 1569 (m), 1487 (s), 1424 (m), 1382 (w), 1369 (s), 1326
[Ag(CH2Cl2)]+};
107/109
(70)
{doublet
(1/1),
[Ag]+}. (m), 1267 (m), 1250 (s), 1218 (s), 1186 (m), 1068 (s), 1077 (m), 1055
1068
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1061–1071

Synthesis and Structure of Silver Amino Arenesulfonates
(s), 984 (m), 934 (w), 918 (m), 842 (m), 814 (s), 802 (m), 751 (s),
(15) {doublet (1/1 107Ag/109Ag), [Ag(L–NH2)]+}; 185/187 (100)
709 (s), 629 (s), 575 (s), 537 (m), 515 (s), 466 (m), 426 (m), 410 (m) {doublet (1/1 107Ag/109Ag), [Ag(DMSO)]+}; 107/109 (30) {doublet
cm–1. FTIR (Nujol): ν = 3437 (s), 3351 (s), 3094 (m), 1623 (s), 1591
(1/1), [Ag]+}. C6H6AgNO3S (280.046): calcd. C 25.73, H 2.16, N
5.00; found C 25.86, H 2.20, N 4.78.
˜
(m), 1561 (w), 1487 (m), 1320 (w), 1274 (m), 1210 (s), 1175 (s),
1056 (s), 988 (m), 969 (w), 956 (w), 944 (w), 926 (w), 843 (m), 831
(m), 814 (m), 763 (s), 705 (m), 624 (m) cm–1. ESI-MS+ (DMSO/
MeOH): m/z (%) = 373/375 (10) {doublet (1/1 107Ag/109Ag),
[AgL(LH)(DMSO)2(MeOH)2 + 2H]2+}; 368/370/372 (5) {triplet (1/
2/1 107Ag/107/109Ag/109Ag), [Ag2L(LH)(MeOH)2(H2O) + Na]2+};
356/358 (5) {doublet (1/1 107Ag/109Ag), [AgL(H2O) + Na]+}; 341/
343 (80) {doublet (1/1 107Ag/109Ag), [AgL(LH)(DMSO)2 + 2H]2+};
[Ag(O3SP)]ϱ (9): 2-Pyridinesulfonic acid was applied to the general
procedure to yield colourless crystalline blocks (264 mg, 99%) suit-
able for X-ray crystallography; m.p. Ͼ 245 °C (decomp.). 1H NMR
3
(300 MHz, [D6]DMSO, 30 °C): δ = 8.60 (d, J = 3.0 Hz, 1 H, H3),
8.05 (td, 3J = 3.0, 9.0 Hz, 1 H, H5), 7.95 (d, 3J = 9.0 Hz, 1 H, H6),
7.58 (m, 1 H, H4) ppm. 13C NMR (100 MHz, [D6]DMSO, 30 °C):
δ = 162.18 (C1), 149.91 (C5), 139.53 (C3), 125.24 (C4), 121.35 (C6)
317/319 (40) {doublet (1/1 107Ag/109Ag), [AgL(LH)(H2O)6
+
ppm. FTIR (KBr): ν = 3422 (m), 1617 (w), 1579 (m), 1458 (m),
˜
2H]2+}; 295/297 (15) {doublet (1/1 107Ag/109Ag), [AgL(LH)-
(MeOH)2 + 2H]2+}; 290/2920 (50) {doublet (1/1 107Ag/109Ag),
[AgL(LH)(H2O)3 + 2H]2+}; 263/265 (100) {[AgL(LH) + 2H]2+}.
C9H8AgNO4S (334.093): calcd. C 32.35, H 2.41, N 4.19; found C
32.03, H 2.40, N 4.15.
1425 (m), 1291 (w), 1208 (s), 1164 (m), 1093 (m), 1049 (m), 1040
(m), 994 (m), 777 (m), 747 (m), 645 (s), 618 (m), 566 (m), 556 (m)
cm–1. FTIR (Nujol): ν = 3394 (w), 1634 (w), 1584 (w), 1429 (m),
˜
1294 (w), 1256 (m), 1232 (m), 1207 (s), 1165 (s), 1146 (s), 1094 (m),
1049 (s), 1019 (m), 1005 (m), 7778 (m), 736 (m), 628 (m) cm–1. ESI-
MS+ (solvent: CH2Cl2): m/z (%) = 456/458/460 (5) {triplet (1/2/1
107Ag/107/109Ag/109Ag), [Ag2L(CH2Cl2)]+}; 372/374/376 (10) {triplet
(1/2/1 107Ag/107/109Ag/109Ag), [Ag2L]+}; 191/193 (100) {doublet
(1/1 107Ag/109Ag), [Ag(CH2Cl2)]+}; 107/109 (60) {doublet (1/1),
[Ag]+}. C5H4AgNO3S (266.022): calcd. C 22.57, H 1.52, N 5.27;
found C 22.77, H 1.40, N 5.22.
[Ag(O3SBAp)]ϱ (8): The general procedure was carried out with p-
aminobenzenesulfonic acid as ligand to yield amber crystalline
blocks (278 mg, 99%) suitable for X-ray crystallography; m.p.
Ͼ 250 °C (decomp.). 1H NMR (300 MHz, [D6]DMSO, 30 °C): δ =
3
3
7.33 (d, J = 8.6 Hz, 2 H, H2 and H6), 6.58 (d, J = 6.4 Hz, 2 H,
H3 and H5) ppm. 13C NMR (75 MHz, [D6]DMSO, 30 °C): δ =
149.91 (C1), 135.56 (C4), 127.72 (C2 and C6), 114.66 (C3 and C5)
X-ray Crystallography: Crystalline samples of 1, 2, 4a and 4b were
ppm. FTIR (KBr): ν = 3469 (m), 3320 (s), 3268 (s), 3185 (s), 1905 mounted onto a glass fibre in viscous hydrocarbon oil. Crystal data
˜
(w), 1600 (s), 1498 (s), 1437 (s), 1332 (w), 1298 (w), 1248 (m), 1197 were collected with either an Enraf–Nonius Kappa CCD or a
(s), 1183 (s), 1152 (s), 1124 (s), 1032 (s), 1000 (s), 945 (s), 841 (m),
Bruker X8 APEX CCD instrument with monochromated Mo-Kα
radiation, λ = 0.71073 Å. All data were collected at 123 K, main-
tained using an open flow of nitrogen from an Oxford Cryostreams
826 (s), 692 (s), 568 (s) cm–1. FTIR (Nujol): ν = 3319 (m), 3267
˜
(m), 3184 (m), 1714 (w), 1599 (m) 1498(m), 1304 (w), 1249 (w),
1186 (s), 1153 (s), 1123 (s), 991 (s), 946 (m), 843 (w), 827 (m), 691 cryostat. X-ray data were processed with the DENZO program.[15]
(m), 569 (s) cm–1. ESI-MS+ (solvent: DMSO/MeOH): m/z (%) =
Structural solution and refinement was carried out using
944/946/948/950/952 (5) {quintet (1/4/6/4/1 107Ag/3ϫ107/109Ag/
SHELXL-97[16] with the graphical interface X-Seed.[17] Data were
3ϫ109/107Ag/2ϫ107/2ϫ109Ag/109Ag), [Ag4L3]+}; 743/745/747/749 (5) corrected for absorption using the SADABS[18] package. The re-
{quartet (1/3/3/1 107Ag/2ϫ107/109Ag/2ϫ109/107 109
(DMSO)]+}; 665/667/669/671 (5) {quartet (1/3/3/1 107Ag/2ϫ107/ niques on F2, minimizing the function (Fo – Fc)2, for which the
109Ag/2ϫ109/107 109Ag), [Ag3L2]+}; 542/544/546 (5) {triplet (1/2/1 weight is defined as 4F2o/2Fo(2) and Fo and Fc are the observed and
107Ag/107/109Ag/109Ag), [Ag2L(DMSO)2]+}; 464/466/468 (10) calculated structure factor amplitudes using the program
{triplet (1/2/1 107Ag/107/109Ag/109Ag), [Ag2L(DMSO)]+}; 263/265 SHELXL-97.[16] During the refinement of 2, the Flack parameter
/
Ag), [Ag3L2- finements were carried out by using full-matrix least-squares tech-
/
Table 4. Crystallographic data and structure refinement for compounds 1, 2, 4a and 4b.
1
2
4a
4b
Formula
Mr
C6H6AgNO3S
280.05
C6H6AgNO3S
280.05
C10H10AgNO4S
348.12
C10H8AgNO3S·H2O
348.12
Crystal size [mm]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
0.28ϫ0.16ϫ0.13
monoclinic
P21/c (no. 14)
5.5730(11)
17.435(4)
7.8510(16)
90
0.42ϫ0.26ϫ0.23
orthorhombic
P212121 (no. 19)
5.7400(11)
8.3240(17)
16.477(3)
90
0.21ϫ0.23ϫ0.15
monoclinic
P21 (no. 4)
7.2689(15)
7.5693(15)
9.6200(19)
90
0.45ϫ0.15ϫ0.30
monoclinic
C2/c (no. 15)
22.4750(5)
7.4410(15)
14.5490(3)
90
β [°]
108.43(3)
90
723.7(3)
4
90
90
787.3(3)
4
104.48(3)
90
512.47(18)
2
123.05(3)
90
2039.4(10)
8
γ [°]
V [Å3]
Z
T [K]
123(2)
2.570
3.030
123(2)
2.363
2.785
123(2)
2.256
2.171
123(2)
2.268
2.182
ρcalcd. [gcm–1]
µ [mm–1]
Reflections collected/unique
Flack x
Rint
7215/1713
–
0.0593
22987/3402
0.50(2)
0.0394
2423/2037
0.18(6)
0.0528
28377/3861
–
0.0371
R1 [IϾ2σ(I)]
wR2 (all data)
GoF
0.0368
0.0909
1.177
0.0315
0.0467
1.059
0.0580
0.1417
1.059
0.0335
0.0598
1.084
Eur. J. Inorg. Chem. 2012, 1061–1071
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1069

M. Busse, P. C. Andrews, P. C. Junk
FULL PAPER
1773; x) M. Sebastian, H. K. Y. John, J. V. Jagadese, J. Chem.
Soc. Dalton Trans. 2002, 4561.
was 0.5, which was not due to missing symmetry. Therefore the
data was refined as a racemic twin. The final values of refinement
parameters are given in Table 4.
[3]
a) X.-H. Bu, H. Liu, M. Du, K. M.-C. Wong, V. W.-W. Yam,
M. Shionoya, Inorg. Chem. 2001, 40, 4143; b) Y.-B. Dong, J.-
Y. Cheng, R.-Q. Huang, Inorg. Chem. 2003, 42, 5699; c) Y.-B.
Dong, J.-P. Ma, R.-Q. Huang, Inorg. Chem. 2003, 42, 294; d)
R. P. Feazell, C. E. Carson, K. Klausmeyer, Inorg. Chem. 2006,
45, 2635; e) K. A. Hirsch, S. R. Wilson, J. S. Moore, Inorg.
Chem. 1997, 36, 2960; f) C. Kaes, M. W. Hosseini, C. E. F.
Rickard, B. W. Skelton, A. H. White, Angew. Chem. 1998, 110,
970; Angew. Chem. Int. Ed. 1998, 37, 920; g) F.-F. Li, J.-F. Ma,
S.-Y. Song, J. Yang, H.-Q. Jia, N.-H. Hu, Cryst. Growth Des.
2006, 6, 209; h) F.-F. Li, J.-F. Ma, S.-Y. Song, J. Yang, Y.-Y.
Liu, Z.-M. Su, Inorg. Chem. 2005, 44, 9374–9383; i) F.-F. Li,
J.-F. Ma, J. Yang, H.-Q. Jia, N.-H. Hu, THEOCHEM 2006,
787, 106; j) C.-S. Liu, P.-Q. Chen, E.-C. Yang, J.-L. Tian, X.-
H. Bu, Z.-M. Li, H.-W. Sun, Z. Lin, Inorg. Chem. 2006, 45,
5812; k) H.-Y. Liu, H. Wu, J.-F. Ma, S.-Y. Song, J. Yang, Y.-Y.
Liu, Z.-M. Su, Inorg. Chem. 2007, 46, 7299; l) H.-Y. Liu, H.
Wu, J.-F. Ma, J. Yang, Y.-Y. Liu, Dalton Trans. 2009, 7957–
7968; m) K. Matsumoto, Y. Harada, N. Yamada, H. Kurata,
T. Kawase, M. Oda, Cryst. Growth Des. 2006, 6, 1083; n) G.
Smith, B. A. Cloutt, K. A. Byriel, C. H. L. Kennard, Aust. J.
Chem. 1997, 50, 741; o) G. Smith, D. E. Lynch, C. H. L. Ken-
nard, Inorg. Chem. 1996, 35, 2711; p) D. Sun, R. Cao, Y. Sun,
W. Bi, X. Li, Y. Wang, Q. Shi, X. Li, Inorg. Chem. 2003, 42,
7512; q) H. Wu, X.-W. Dong, H.-Y. Liu, J.-F. Ma, S.-L. Li, J.
Yang, Y.-Y. Liu, Z.-M. Su, Dalton Trans. 2008, 5331–5341; r)
S.-P. Yang, X.-M. Chen, L.-N. Ji, J. Chem. Soc. Dalton Trans.
2000, 2337.
CCDC-848459 (for 1), -848460 (for 2), -848461 (for 4a) and
-848462 (for 4b) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Acknowledgments
We thank the Australian Research Council and Monash University
for funding.
[1] a) U. S. Agarwal, S. Thampi, A. K. Jain, Reliance Industries
Limited, India, 2009, PCT Int. Appl. WO 2009072144; b) D.
Baram-Pinto, S. Shukla, N. Perkas, A. Gedanken, R. Sarid,
Bioconjugate Chem. 2009, 20, 1497–1502; c) X. Cao, M. Tang,
F. Liu, Y. Nie, C. Zhao, Colloids Surf. B: Biointerfaces 2010,
81, 555–562; d) T. Kawakami, S. Teshima, Y. Asako, H. Tsuboi,
Nippon Shokubai Kagaku Kogyo Co., Ltd., Japan, 1997, Jpn.
Kokai Tokkyo Koho JP 09301812; e) K. Shirai, Y. Ishii, S.
Nomura, S. Shoji, O. Suzuki, T. Sato, Nippi Inc., Japan, 2002,
Jpn. Kokai Tokkyo Koho JP 2002220311; f) L. Stephen, Spe-
cialty Fibres and Materials Limited, UK, 2010, PCT Int. Appl.
WO 2010061225; g) D. Vachon, G. E. Wnek, Aegis Biosciences,
LLC, USA, 2001, US Pat. Appl. US 6306419; h) K. Vasilev,
V. R. Sah, R. V. Goreham, C. Ndi, R. D. Short, H. J. Griesser,
Nanotechnology 2010, 21, 215102/1–215102/6.
[4]
[5]
Y. Jimbo, E. Takahashi, Y. Shimada, K. Sato, Fujifilm Corpo-
ration, Japan, 2008, Eur. Pat. Appl. EP 1889601.
a) J. Ibata, Y. Shimamura, Asahi Chemical Industry Co., Ltd.,
Japan, 1989, Jpn. Kokai Tokkyo Koho JP 01274129; b) R. A.
Lee, du Pont de Nemours, E. I., and Co., USA, 1985, US Pat.
Appl. US 4504575.
[2] a) A. P. Cote, M. J. Ferguson, K. A. Khan, G. D. Enright,
A. D. Kulynych, S. A. Dalrymple, G. K. H. Shimizu, Inorg.
Chem. 2002, 41, 287; b) A. P. Cote, G. K. H. Shimizu, Inorg.
Chem. 2004, 43, 6663–6673; c) D. J. Hoffart, S. A. Dalrymple,
G. K. H. Shimizu, Inorg. Chem. 2005, 44, 8868–8875; d) S. K.
Makinen, N. J. Melcer, M. Parvez, G. K. H. Shimizu, Chem.
Eur. J. 2001, 7, 5176; e) G. K. H. Shimizu, G. D. Enright, C. I.
Ratcliffe, K. F. Preston, J. L. Reid, J. A. Ripmeester, Chem.
Commun. 1999, 1485–1486; f) G. K. H. Shimizu, G. D. Enright,
C. I. Ratcliffe, G. S. Rego, J. L. Reid, J. A. Ripmeester, Chem.
Mater. 1998, 10, 3282–3283; g) G. K. H. Shimizu, G. D. En-
right, C. I. Ratcliffe, J. A. Ripmeester, Chem. Commun. 1999,
461–462; h) G. Smith, B. A. Cloutt, D. E. Lynch, K. A. Byriel,
C. H. L. Kennard, Inorg. Chem. 1998, 37, 3236–3242; i) F.
Charbonnier, R. Faure, H. Loiseleur, Cryst. Struct. Commun.
1981, 10, 1129; j) C.-H. Chen, J.-W. Cai, X.-L. Feng, X.-M.
Chen, Polyhedron 2002, 21, 689; k) G. Smith, J. H. Thomasson,
J. M. White, Aust. J. Chem. 1999, 52, 317; l) N. J. Melcer, G. D.
Enright, J. A. Ripmeester, G. K. H. Shimizu, Inorg. Chem.
2001, 40, 4641; m) G. K. H. Shimizu, G. D. Enright, G. S.
Rego, J. A. Ripmeester, Can. J. Chem. 1999, 77, 313; n) J.-F.
Ma, J. Yang, S.-L. Li, S.-Y. Song, H.-J. Zhang, H.-S. Wang, K.-
Y. Ya n g , Cryst. Growth Des. 2005, 5, 807; o) A. D. Kulynych,
G. K. H. Shimizu, CrystEngComm 2002, 18, 102; p) G.
Wulfsberg, K. D. Parks, R. Rutherford, D. J. Jackson, F. E.
Jones, D. Derrick, W. Ilsley, S. H. Strauss, S. M. Miller, O. P.
Anderson, T. A. Babushkina, S. I. Gushchin, E. A. Kravch-
enko, V. G. Morgunov, Inorg. Chem. 2002, 41, 2032; q) D. Sun,
R. Cao, Y. Liang, M. Hong, Chem. Lett. 2002, 198; r) D. Sun,
R. Cao, Y. Sun, W. Bi, X. Li, M. Hong, Y. Zhao, Eur. J. Inorg.
Chem. 2003, 38; s) D. Sun, R. Cao, W. Bi, X. Li, Y. Wang, M.
Hong, Eur. J. Inorg. Chem. 2004, 2144; t) L. J. May, G. K. H.
Shimizu, Chem. Mater. 2005, 17, 217; u) P. F. Charbonnier,
Acta Crystallogr. Sect. B: Struct. Crystallogr. Cryst. Chem.
1977, 33, 2824; v) P. F. Charbonnier, R. F. H. Loiseleur, Acta
Crystallogr. Sect. B: Struct. Crystallogr. Cryst. Chem. 1978, 34,
3598; w) P. F. Charbonnier, R. F. H. Loiseleur, Acta Crys-
tallogr. Sect. B: Struct. Crystallogr. Cryst. Chem. 1979, 35,
[6]
a) B. D. Chandler, A. P. Cote, D. T. Cramb, J. M. Hill, G. K. H.
Shimizu, Chem. Commun. 2002, 1900; b) A. P. Cote, G. K. H.
Shimizu, Chem. Commun. 2001, 251; c) A. P. Cote, G. K. H.
Shimizu, Coord. Chem. Rev. 2003, 245, 49–64; d) A. P. Cote,
G. K. H. Shimizu, Chem. Eur. J. 2003, 9, 5361; e) S. A. Dalrym-
ple, M. Parvez, G. K. H. Shimizu, Chem. Commun. 2001, 2672;
f) S. A. Dalrymple, M. Parvez, G. K. H. Shimizu, Inorg. Chem.
2002, 41, 6986; g) S. A. Dalrymple, G. K. H. Shimizu, Chem.
Commun. 2002, 2224; h) S. A. Dalrymple, G. K. H. Shimizu,
Chem. Eur. J. 2002, 8, 3010; i) D. J. Hoffart, A. P. Cote,
G. K. H. Shimizu, Inorg. Chem. 2003, 42, 8603; j) D. S. Reddy,
S. Duncan, G. K. H. Shimizu, Angew. Chem. 2003, 115, 1398;
Angew. Chem. Int. Ed. 2003, 42, 1360; k) J. O. Yu, A. P. Cote,
G. D. Enright, G. K. H. Shimizu, Inorg. Chem. 2001, 40, 582;
l) G. K. H. Shimizu, R. Vaidhyanathan, J. M. Taylor, Chem.
Soc. Rev. 2009, 38, 1430–1449.
a) J. Cai, Coord. Chem. Rev. 2004, 248, 1061–1083; b) J. Cai,
C.-H. Chen, C.-Z. Liao, J.-H. Yao, X.-P. Hu, X.-M. Chen, J.
Chem. Soc. Dalton Trans. 2001, 1137; c) J. W. Cai, C. H. Chen,
X. L. Feng, C. Z. Liao, X. M. Chen, J. Chem. Soc. Dalton
Trans. 2001, 2370; d) J. W. Cai, C. H. Chen, C. Z. Liao, X. L.
Feng, X. M. Chen, Acta Crystallogr. Sect. B 2001, 57, 520; e)
J. W. Cai, J. S. Zhou, M. L. Lin, J. Mater. Chem. 2003, 13,
1806; f) J.-W. Cai, C.-H. Chen, J.-S. Zhou, Chin. J. Inorg. Chem.
2003, 19, 81; g) J.-W. Cai, J.-S. Zhou, M.-L. Lin, J. Mater.
Chem. 2003, 13, 1906; h) C. H. Chen, J. W. Cai, C. Z. Liao,
X. L. Feng, X. M. Chen, S. W. Ng, Inorg. Chem. 2002, 41,
4967; i) J.-S. Zhou, J. Cai, L. Wang, Dalton Trans. 2004, 1493.
[7]
[8]
a) J. L. Atwood, L. J. Barbour, M. J. Hardie, C. L. Raston, Co-
ord. Chem. Rev. 2001, 222, 3; b) R. Custelcean, M. D. Ward,
Angew. Chem. 2002, 114, 1800; Angew. Chem. Int. Ed. 2002,
41, 1724; c) K. T. Holman, A. M. Pivovar, J. A. Swift, M. D.
Ward, Acc. Chem. Res. 2001, 34, 107; d) M. J. Horner, K. T.
Holman, M. D. Ward, Angew. Chem. 2001, 113, 4169; Angew.
1070
www.eurjic.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2012, 1061–1071

Synthesis and Structure of Silver Amino Arenesulfonates
Chem. Int. Ed. 2001, 40, 4045; e) A. R. Kennedy, M. P. Hughes,
M. L. Monaghan, E. Staunton, S. J. Teat, W. E. Smith, J.
Chem. Soc. Dalton Trans. 2001, 2199; f) G. Mezei, R. G.
Rapris, New J. Chem. 2003, 27, 1399; g) S. H. Park, C. E. Lee,
Chem. Commun. 2003, 1838; h) J. A. Swift, M. D. Ward, Chem.
Mater. 2000, 12, 1501; i) X.-L. Zhang, B.-H. Ye, X.-M. Chen,
Cryst. Growth Des. 2005, 5, 1609; j) A. Mietrach, T. W. T.
Muesmann, J. Christoffers, M. S. Wickleder, Eur. J. Inorg.
Chem. 2009, 5328–5334; k) A. Mietrach, T. W. T. Muesmann,
C. Zilinski, J. Christoffers, M. S. Wickleder, Z. Anorg. Allg.
Chem. 2011, 637, 195–200; l) T. W. T. Muesmann, A. Mietrach,
J. Christoffers, M. S. Wickleder, Z. Anorg. Allg. Chem. 2010,
636, 1307–1312; m) T. W. T. Muesmann, C. Zitzer, A. Mie-
trach, T. Kluener, J. Christoffers, M. S. Wickleder, Dalton
Trans. 2011, 40, 3128–3141; n) T. W. T. Muesmann, C. Zitzer,
M. S. Wickleder, J. Christoffers, Inorg. Chim. Acta 2011, 369,
45–48.
Gromilov, Y. A. Dyadin, J. Am. Chem. Soc. 1999, 121, 4179; g)
D. V. Soldatov, P. Tinnemans, G. D. Enright, C. I. Ratcliffe,
P. R. Diamente, J. A. Ripmeester, Chem. Mater. 2003, 15, 3826;
h) L. C. Tabares, J. A. R. Navarro, J. M. Salas, J. Am. Chem.
Soc. 2001, 123, 393; i) K. Uemura, S. Kitagawa, K. Fukui, K.
Saito, J. Am. Chem. Soc. 2004, 126, 3817; j) K. Uemura, S.
Kitagawa, M. Kondo, K. Fukui, R. Kitaura, H. C. Chang, T.
Mizutani, Chem. Eur. J. 2002, 8, 3586; k) J. J. Vittal, X. Yang,
Cryst. Growth Des. 2002, 2, 259.
[11] a) Z.-P. Deng, L.-H. Huo, M.-S. Li, L.-W. Zhang, Z.-B. Zhu,
H. Zhao, S. Gao, Cryst. Growth Des. 2011, 11, 3090–3100; b)
Z.-P. Deng, M.-S. Li, Z.-B. Zhu, L.-H. Huo, H. Zhao, S. Gao,
Organometallics 2011, 30, 1961–1967; c) Z.-P. Deng, Z.-B. Zhu,
S. Gao, L.-H. Huo, H. Zhao, Dalton Trans. 2009, 38, 1290–
1292; d) Z.-P. Deng, Z.-B. Zhu, S. Gao, L.-H. Huo, H. Zhao,
S. W. Ng, Dalton Trans. 2009, 38, 6552–6561.
[12] a) A. Leon, Historia Natural das Doencas Mexico, Mexico
1992, Centro de Documentacion Institucional, p. 782; b) Y.-J.
Pan, F.-J. Meng, X.-J. Wang, H.-L. Zhu, D.-Q. Wang, Z. Kris-
tallogr. New Cryst. Struct. 2003, 218, 253–254; c) J. Schreuer,
Z. Kristallogr. New Cryst. Struct. 1999, 214, 311–312; d) O.
Sadeghi, M. M. Amini, S. W. Ng, Acta Crystallogr. Sect. E
Struct. Rep. Online 2010, 66, m855–m856; e) F. R. Ahmed,
D. W. J. Cruickshank, Acta Crystallogr. 1952, 5, 852.
[13] M. Tanabe, R. H. Peters, Org. Synth. Coll. Vol. 1990, 7.
[14] J. W. Steed, J. L. Atwood, Supramolecular Chemistry, Wiley,
Toronto, 2000, p. 19.
[9] a) G. Alberti, U. Constantino, in: Inclusion Compounds. (Eds.:
J. L. Atwood, J. E. D. Davis, D. D. MacNicol), Oxford Univer-
sity Press, New York, 1991, vol. 5, p. 136; b) G. Alberti, U.
Constantino in Comprehensive Supramolecular Chemistry
(Eds.: G. Alberti, T. Bein), Elsevier Science, New York, 1996,
vol. 7; c) A. Clearfield, Prog. Inorg. Chem. 1998, 47, 371; d)
C. P. Johnson, J. L. Atwood, J. W. Steed, C. B. Bauer, R. D. Ro-
gers, Inorg. Chem. 1996, 35, 2602; e) E. J. Kosnic, E. L. McCly-
mont, R. A. Hodder, P. J. Squattrito, Inorg. Chim. Acta 1992,
201, 143.
[10] a) B. F. Abrahams, M. J. Hardie, B. F. Hoskins, R. Robson,
G. A. Williams, J. Am. Chem. Soc. 1992, 114, 10641; b) K.
Biradha, M. Fujita, Angew. Chem. 2002, 114, 3542; Angew.
Chem. Int. Ed. 2002, 41, 3392; c) K. Biradha, Y. Hongo, M.
Fujita, Angew. Chem. 2002, 114, 3545; Angew. Chem. Int. Ed.
2002, 41, 3395; d) C. J. Kepert, T. J. Prior, M. J. Rosseinsky, J.
Am. Chem. Soc. 2000, 122, 5158; e) Z.-X. Lian, J. Cai, C.-H.
Chen, Polyhedron 2007, 26, 2647–2654; f) D. V. Soldatov, J. A.
Ripmeester, S. I. Shergina, I. E. Sokolov, A. S. Zanina, S. A.
[15] Z. Otwinowski, W. Minor, Methods Enymol. 1997, 276, 307.
[16] G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112.
[17] L. J. Barbour, XSEED: A graphical interface for use with the
SHELX97 program suite, University of Missouri, USA, 1999.
[18] G. M. Sheldrick, SADABS, Program for area detector adsorp-
tion correction, Institute for Inorganic Chemistry, University of
Göttingen, Germany, 1996.
Received: October 14, 2011
Published Online: January 31, 2012
Eur. J. Inorg. Chem. 2012, 1061–1071
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1071