Synthesis, crystal structures, spectroscopic and thermal properties of silver(I) saccharinate complexes with N-donor ligands

Article abstract of DOI:10.1016/j.poly.2012.05.034

The synthesis, spectroscopic and thermal properties and X-ray structures of four silver(I) saccharinate complexes with N-donor ligands, [Ag(sac)(edmen)] (1), [Ag(sac)(teten)] (2), [Ag₂(sac)₂(o-bix)₂] (3) and [Ag(sac)(dpa)] (4) (edmen = N-ethyl-N′,N′- dimethylethylenediamine, teten = N,N,N′,N′-tetrakis(2-hydroxyethyl) ethylenediamine, o-bix = 1,2-bis(imidazole-1-ylmethyl)benzene and dpa = 2,2′-dipyridylamine) are described. In complex 1, the Ag(I) ion is coordinated by two N atoms from edmen and one N atom from sac ligand, forming a slightly distorted Y-shaped AgN₃ arrangement. In complex 2, the Ag(I) is four coordinated by N-bonded sac and tridentate teten ligands, exhibiting a seesaw AgN₃O geometry. A crystallographically independent Ag(I) ion in 3 is surrounded with a T-shaped geometry by two N atoms from o-bix ligand and one N atom from one sac ligand, and the Ag?Ag separation is 3.338 ?. In complex 4, the Ag1 ion is coordinated by three nitrogen atoms from sac and dpa ligands to form a distorted Y-shaped geometry. The dpa ligand behaves as a bidentate ligand, forming a six-membered chelate ring, while the sac ligand is N-coordinated. The most striking feature of complexes 1 and 2 is the presence of both intra- and intermolecular C-H?Ag hydrogen-bonding interactions. Crystal packing of complexes is achieved by the hydrogen bonds, intra- and/or intermolecular C-H?π, weak π?π and Ag?π interactions to generate a three-dimensional supramolecular network. The photoluminescence spectrum shows that 4 displays a red-shift emission in the solid state at room temperature.

Full text of DOI:10.1016/j.poly.2012.05.034

Polyhedron 42 (2012) 307–314
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis, crystal structures, spectroscopic and thermal properties of silver(I)
saccharinate complexes with N-donor ligands
a,
⇑
a
a,b
a
Okan Zafer Ye ßs ilel , Bingül Karamahmut , Fatih Semerci , Ye ßs im Ye ßs ilöz
a
Department of Chemistry, Faculty of Arts and Sciences, Eski ßs ehir Osmangazi University, 26480 Eski ßs ehir, Turkey
Department of Chemistry, Faculty of Arts and Sciences, Kırklareli University, 39300 Kırklareli, Turkey
b
a r t i c l e i n f o
a b s t r a c t
Article history:
The synthesis, spectroscopic and thermal properties and X-ray structures of four silver(I) saccharinate
complexes with N-donor ligands, [Ag(sac)(edmen)] (1), [Ag(sac)(teten)] (2), [Ag (sac) (o-bix) ] (3) and
Received 28 March 2012
Accepted 30 May 2012
Available online 9 June 2012
2
2
2
0
0
0
0
[
Ag(sac)(dpa)]
(4)
(edmen = N-ethyl-N ,N -dimethylethylenediamine,
teten = N,N,N ,N -tetrakis(2-
0
hydroxyethyl)ethylenediamine, o-bix = 1,2-bis(imidazole-1-ylmethyl)benzene and dpa = 2,2 -dipyridyl-
amine) are described. In complex 1, the Ag(I) ion is coordinated by two N atoms from edmen and one
Keywords:
N atom from sac ligand, forming a slightly distorted Y-shaped AgN
Ag(I) is four coordinated by N-bonded sac and tridentate teten ligands, exhibiting a seesaw AgN
3
arrangement. In complex 2, the
O geom-
Saccharinate complexes
Silver complexes
C–Hꢀ ꢀ ꢀAg interaction
3
etry. A crystallographically independent Ag(I) ion in 3 is surrounded with a T-shaped geometry by two N
atoms from o-bix ligand and one N atom from one sac ligand, and the Agꢀ ꢀ ꢀAg separation is 3.338 Å. In
complex 4, the Ag1 ion is coordinated by three nitrogen atoms from sac and dpa ligands to form a dis-
torted Y-shaped geometry. The dpa ligand behaves as a bidentate ligand, forming a six-membered chelate
ring, while the sac ligand is N-coordinated. The most striking feature of complexes 1 and 2 is the presence
of both intra- and intermolecular C–Hꢀ ꢀ ꢀAg hydrogen-bonding interactions. Crystal packing of complexes
is achieved by the hydrogen bonds, intra- and/or intermolecular C–Hꢀ ꢀ ꢀ
p
, weak
p
ꢀ ꢀ ꢀ
p
and Agꢀ ꢀ ꢀ
p interac-
tions to generate a three-dimensional supramolecular network. The photoluminescence spectrum shows
that 4 displays a red-shift emission in the solid state at room temperature.
Ó 2012 Elsevier Ltd. All rights reserved.
1
. Introduction
Improvement on the field of supramolecular chemistry is criti-
relationships. Among the polymeric coinage d10 metal complexes,
silver(I) coordination polymers have received much attention be-
cause silver(I), as a soft acid, coordinating to soft bases such as S-
and N-containing ligands is an advantageous building block for
coordination compounds with unique metal–carbon and metal–
metal interactions [10–15]. However, other non-classical hydrogen
bonding, such as agostic and anagostic X–Hꢀ ꢀ ꢀM interactions
(X = C, N and O; M = Ti, Ni, Cu, Pd, Mo, etc.), have been somewhat
less documented [6,16–18]. To the best of our knowledge, so far
a few supramolecular complexes containing C–Hꢀ ꢀ ꢀAg close inter-
actions have been designed and reported [19,20].
Saccharinate (sac) is a well-known versatile ligand that has
been widely used in the synthesis of complexes [21–27]. Sac ligand
coordinates to metal ions by means of its two sulfonyl oxygen
atoms, one carbonyl oxygen atom and one imino nitrogen atom
cally dependent on the ease information can be gathered from
studies on coordination compounds in the solid state [1–3]. The
design, synthesis, and characterization of metallosupramolecular
architectures have attracted considerable attention in supramolec-
ular chemistry because of their structural diversity and potential
applications in host–guest chemistry, catalysis, electrical conduc-
tivity and magnetism [4–7]. Non-covalent bonding interactions in-
clude hydrogen bonds,
pꢀ ꢀ ꢀ
p
, C–Hꢀ ꢀ ꢀ
p are widely used to generate
metallosupramolecular systems. These interactions have been ap-
proved by theoretical investigations and single-crystal structures
during the past 20 years [4–7]. Hydrogen-bonding interaction can
be used to predict and design supramolecular assemblies in one-,
two- and three-dimension [8,9].
The progress of crystal engineering is related to understanding
of intermolecular interactions and functional materials can only
be designed with a better understanding of structure function
forming monodentate, bidentate, bis(monodentate) bridge (
bis(bidentate) bridge ( ), tridentate bridge ( and ), tetraden-
tate bridge ( ) ligand [23]. In addition to these donor atoms, a sac
2
l ),
l
2
l
2
l
3
l
2
may be regarded as a hydrogen bonding acceptor with a significant
potential to generate supramolecular assemblies in the solid state.
Until now, the crystal structures of many mixed-ligand Ag(I)-sac
complexes with N-, O- or S-donor ligands have been reported
⇑
Corresponding author. Tel.: +90 2222393750; fax: +90 2222393578.
E-mail address: yesilel@ogu.edu.tr (O.Z. Ye sß ilel).
[
22,28–33].
0
277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.05.034

3
08
O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
Table 1
Selected IR spectral data for 1–4 (cmꢁ1).
Assignment
[Ag(sac)] [49]
[Ag(sac)(edmen)] (1)
[Ag(sac)(teten)] (2)
2
[Ag (sac)
2 2
(o-bix) ] (3)
[Ag(sac)(dpa)] (4)
m
m
m
m
m
m
m
(OH)
(NH)
(CO)
(CC)
–
–
–
3387 m
–
1639vs, 1624vs
1583s, 1458 m
1334 m
–
–
–
3227s
1645vs
1587s, 1458s
1329sh
1301vs, 1258vs
1155vs
3309s
1640sh, 1612vs
1577vs, 1458s
1338sh
1284vs, 1258vs
1150vs
1639vs
1583vs, 1454 m
1328sh
1251vs
1147vs
1643vs
1533vs, 1477 m
1381 m
1287vs
1152vs
s
(CNS)
as(SO
(SO
2
)
1267vs
1151vs
s
2
)
sh = shoulder; w = weak; m = medium; s = strong; vs = very strong.
As a part of our continuing research on the syntheses and char-
acterizations of Ag(I)-saccharinate complexes, in this study, we re-
port the syntheses, spectroscopic and thermal studies (TG, DTG and
DTA) and crystal structures of four Ag(I)-sac complexes with
2.2. Crystallographic analyses
Crystallographic data 1 and 2 were recorded on a Bruker Kappa
APEXII CCD area-detector diffractometer, 3 was recorded on a four-
circle Rigaku R-AXIS RAPID-S diffractometer equipped with a two-
dimensional area IP detector and crystallographic data 4 was re-
0
0
0
0
N-ethyl-N ,N -dimethylethylenediamine (edmen), N,N,N ,N -tetra-
kis(2-hydroxyethyl)ethylenediamine (teten), 1,2-bis(imidazole-1-
0
ylmethyl)benzene (o-bix) and 2,2 -dipyridylamine (dpa) ligands,
corded on a SuperNova Eos diffractometer using Mo Ka radiation
[
Ag(sac)(edmen)] (1), [Ag(sac)(teten)] (2), [Ag
2
(sac)
2
(o-bix)
2
] (3)
(k = 0.71073 Å). Absorption corrections by multi-scan were ap-
plied. The structures were solved by direct methods using the pro-
gram OLEX2 [35] and SHELXS-97 [36] with anisotropic thermal
parameters for all non-hydrogen atoms. All non-hydrogen atoms
were refined anisotropically by full-matrix least-squares methods
SHELXL-97 [36]. The four 2-hydroxyethyl groups of teten ligand in
complex 2 shows positional disorder with 50% occupancy factor.
Molecular drawings were obtained using MERCURY [37].
and [Ag(sac)(dpa)] (4). Moreover, photoluminescence properties
of 4 and dpa ligand were recorded in the solid state at the room
temperature.
2
. Experimental
2.1. Materials and instrumentation
2.3. Synthesis of complexes
The o-bix ligand was synthesized according to the method re-
ported previously [34], and all other chemicals were used as com-
mercially available. The IR absorption spectra were recorded in the
2.3.1. [Ag(sac)(edmen)] (1)
A solution of Na(sac)ꢀH
2
O (0.99 g, 4.83 mmol) in water (10 mL)
3
was added dropwise with stirring to a solution of AgNO (0.820 g,
ꢁ1
range of 400–4000 cm by means of a Bruker Tensor 27 FT-IR
spectrometer with KBr pellets. Elemental analyses for C, H, and N
4.83 mmol) in water (10 mL). Then, a suspension with a white pre-
cipitate formed and the addition of edmen (0.427 g, 3.68 mmol) in
methanol–water (1:1, 10 mL) to the suspension resulted in a clear
solution. The resultant solution was allowed to slowly evaporate in
darkness at room temperature. The red-brown single crystals of 1
obtained in one week filtered and washed with 5 mL of ethanol and
_
were carried out at the TÜBITAK Marmara Research Centre. Perkin
Elmer Diamond TG/DTA thermal analyzer was used to record
simultaneous TG, DTG and DTA curves in the static air atmosphere
ꢁ1
at a heating rate of 10 °C min in the temperature range 30–
00 °C using platinum crucibles. The photoluminescence spectra
7
for the complex 4 and dpa ligand were determined with a Per-
kin-Elmer LS-55 spectrophotometer.
dried in air. Elemental analysis: Anal. Calc. for C13
38.43; H, 4.96; N, 10.34. Found: C, 38.40; H, 5.02; N, 10.27%.
3 3
H20AgN O S: C,
Table 2
Crystallographic data and structure refinement parameters for complexes 1–4.
Complexes
1
2
3
4
Empirical formula
Formula weight
T (K)
C
13
H
20AgN
3
O
3
S
C
17
H
28AgN
3
O
7
S
C
42
H
36Ag
2
N
10
O
S
6 2
C
17 4 3
H13AgN O S
406.25
100
526.35
293
1056.69
293
461.24
293
Wavelength (Å)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
0.71073, Mo Ka
monoclinic
P2 /c
monoclinic
P2 /n
7.8823(5)
20.9936(12)
12.6263(8)
93.626(6)
2085.2(2)
4
monoclinic
P2 /n
10.0540(2)
16.0298(2)
13.8354(3)
109.6172(12)
2100.34(7)
2
monoclinic
P2 /n
6.9385(3)
18.6055(7)
13.2694(6)
102.123(5)
1674.80(12)
4
1.36
1
1
1
1
11.8593(2)
12.9366(2)
10.5564(2)
95.598(1)
1611.83(5)
4
b (°)3
V (Å )
Z
l
D
(mm 1
ꢁ
)
1.39
1.674
1.11
1.677
1.09
1.671
calc (mg mꢁ3)
1.829
h range (°)
Measured reflections
Independent reflections
2.5–28.4
16029
4043
3.2–27.9
8355
4178
2.5–26.4
43457
4330
3.2–28.78
13295
3968
R
int
0.026
0.021, 0.056
1.06
0.56, ꢁ0.69
0.017
0.069, 0.184
1.04
1.43, ꢁ1.43
0.097
0.048, 0.108
1.03
0.43, ꢁ0.48
0.095
0.062, 0.142
1.04
0.86, ꢁ0.66
2
2
2
R[F > 2
Goodness-of-fit on F
D
r
(F )], wR(F )
2
ꢁ
3
q
max
,
D
q
min (e Å
)

O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
309
2
.3.2. [Ag(sac)(teten)] (2)
The synthesis of 2 was similar to that of 1, but with teten
0.87 g, 3.68 mmol) in place of edmen. Lilac-colored crystals of 2
were obtained. Elemental analysis: Anal. Calc. for C17 28AgN S:
C, 38.79; H, 5.36; N, 7.98; O, 21.28; S, 6.09. Found: C, 38.61; H,
.54; N, 7.97%.
(
H
3 7
O
5
2
.3.3. [Ag
The synthesis of 3 was similar to that of 1, but with o-bix
0.97 g, 3.68 mmol) in place of edmen with stirring at 80 °C for
h. Suitable gray crystals of 3 were obtained. Elemental analysis:
Anal. Calc. for C21 18AgN S: C, 47.74; H, 3.43; N, 13.26. Found:
C, 47.88; H, 3.46; N, 13.18%.
2 2 2
(sac) (o-bix) ] (3)
(
3
H
5 3
O
2.3.4. [Ag(sac)(dpa)] (4)
The synthesis of 4 was similar to that of 1, but with dpa (0.83 g,
.83 mmol) in 10 mL methanol in place of edmen with stirring at
0 °C for 3 h. Then, a few drops of ammonia were added to this sus-
4
8
pension until a clear solution resulted. The resultant solution was
allowed to evaporate slowly in darkness at room temperature for
one week to give colorless single crystals of 4. Elemental analysis:
Anal. Calc. for C17
4 3
H13AgN O S: C, 44.27; H, 2.84; N, 12.15. Found: C,
i
4
4.21; H, 2.86; N, 12.23%.
Fig. 1. The molecular structure of 1 with intermolecular C–Hꢀ ꢀ ꢀAg and N1–H1ꢀ ꢀ ꢀO1
hydrogen bonding interactions ((i) x, ½ ꢁ y, ꢁ½ + z).
Table 3
Selected bond distances and bond angles (Å, °) for complexes 1–4.
Bond distances (Å)
Bond angles (°)
Complex 1
Ag1–N1
Ag1–N2
Ag1–N3
Complex 2
Ag1–N1
Ag1–N2
Ag1–N3
Complex 3
Ag–N3
2.219(1)
2.459(1)
2.115(1)
N1–Ag1–N2
N3–Ag1–N1
N3–Ag1–N2
77.97(5)
156.49(5)
125.21(5)
2.223(5)
2.417(5)
2.454(5)
N1–Ag1–N2
N1–Ag1–N3
N3–Ag1–N2
144.37(19)
133.62(19)
77.31(18)
2.130(4)
2.116(3)
2.671(3)
3.338(1)
N1–Ag–N3
168.70(1)
98.10(9)
87.96(9)
i
Ag–N1
N1–Ag–Ag
N3–Ag–Ag
i
Ag1–N5
i
Ag–Ag
Complex 4
Ag1–N1
Ag1–N2
Ag1–N4
2.122(5)
2.298(5)
2.250(5)
N1–Ag1–N4
N1–Ag1–N2
N4–Ag1–N2
143.1(2)
133.7(2)
83.1(2)
Symmetry code: (i) ꢁx + 1, ꢁy, ꢁz + 1.
Table 4
Selected geometric parameters for complexes 1–4.
Hydrogen bonding geometry
D–Hꢀ ꢀ ꢀA
d(D–H)
d(Hꢀ ꢀ ꢀA)
d(Dꢀ ꢀ ꢀA)
\(DHA)
Complex 1
i
Fig. 2. The molecular structure of 2 with intramolecular O–Hꢀ ꢀ ꢀAg and O–Hꢀ ꢀ ꢀO
N1–H1ꢀ ꢀ ꢀO1
0.85
0.98
0.98
2.12
2.871
3.004
2.924(2)
3.401(2)
3.564(2)
156
50.0(1)
117.5(1)
hydrogen bonding interactions.
C2–H2Aꢀ ꢀ ꢀAg1
i
C6–H6Cꢀ ꢀ ꢀAg1
Complex 2
O4–H4Aꢀ ꢀ ꢀO1
0.82
0.82
0.99(2)
0.82
2.08
2.10
1.91(5)
2.43
2.812(13)
2.749(16)
2.799(7)
149
136
147(7)
123
3
. Result and discussion
O5B–H5Bꢀ ꢀ ꢀO4B
i
O7–H7ꢀ ꢀ ꢀO1
O6A–H6Aꢀ ꢀ ꢀO3
2.949(13)
3.1. Crystal structure
Complex 3
C16–H16ꢀ ꢀ ꢀO2
Complex 4
N3–H3ꢀ ꢀ ꢀO1
0.93
0.86
2.44
2.04
3.2292
142
173
The crystal data and the refinement details of complexes are gi-
ven in Table 2. Selected bond distances, bond angles and hydrogen
bonding geometry are listed in Tables 3 and 4, respectively. The
X-ray structural analysis reveals that the molecular structure of
i
2.892(7)
Symmetry codes: (i) x, ½ ꢁ y, ꢁ½ + z for 1, (i) x ꢁ 1, y, z for 2, (i) ꢁx, ꢁy, ꢁz + 1 for 4.

3
10
O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
of the edmen ligand has also been observed, which further linked
the neighboring complex unit to generate a 1D supramolecular
chain structure with Ag1ꢀ ꢀ ꢀH6C distance of 3.004 Å, the Ag1ꢀ ꢀ ꢀC6
distance of 3.564(2) Å and C6–H6Cꢀ ꢀ ꢀAg1 angle of 117.5(1)°
(Fig. 1). This weak hydrogen bonding plays a crucial role in con-
structing the supramolecular network (Fig. 1). This kind of C–
Hꢀ ꢀ ꢀAg interaction in 1 can be well described as being of a weak
intermolecular C–Hꢀ ꢀ ꢀM hydrogen bonding based on the bond pre-
viously reported bond parameter comparisons [18,44].
The crystal structure of 2 consists of a neutral [Ag(sac)(teten)]
molecule (Fig. 2). The silver is four coordinated by N-bonded sac
3
and tridentate teten ligands, exhibiting a seesaw AgN O geometry.
X-ray structural analysis show that there are C–Hꢀ ꢀ ꢀAg hydrogen-
bonding interactions between the Ag(I) ion, H12C and H10B atom
of teten ligand (Fig. 3). The Ag1ꢀ ꢀ ꢀH10B and Ag1ꢀ ꢀ ꢀH12C and the
distances of 2.573 and 2.917 Å, Ag1ꢀ ꢀ ꢀC10A and Ag1ꢀ ꢀ ꢀC12A dis-
tances of 3.277 and 3.262 Å, respectively [d(Agꢀ ꢀ ꢀH) < d(Agꢀ ꢀ ꢀC)].
The C10A–H10Bꢀ ꢀ ꢀAg1 and the C12A–H12Cꢀ ꢀ ꢀAg1 angles of
1
30.08° and 102.53°, respectively [C–Hꢀ ꢀ ꢀAg > 100°] are similar to
Fig. 3. View of the O–Hꢀ ꢀ ꢀAg, C–Hꢀ ꢀ ꢀAg, C–Hꢀ ꢀ ꢀ
p and hydrogen bonding
those values for reported Ag(I) complexes [40–42].
interactions.
The crystal packing in 2 displays strong hydrogen bonding
interactions (Fig. 3). The neighboring complex units are connected
through O–Hꢀ ꢀ ꢀO hydrogen bonds to form 2-D layer structure in ac
plane (Fig. 3). The OH groups of teten ligand are involved both in-
tra- and intermolecular hydrogen bond with the carbonyl O and
complex 1 consists of one Ag(I) ion, one sac and one edmen ligands,
as shown in Fig. 1. The Ag1 is coordinated by three N atoms from
an edmen ligand displaying a chelating coordination mode and a
sac ligand, having an in a slightly distorted Y-shaped geometry.
These bonds distances are comparable to the distances found in
other silver complexes of the saccharinate ligand [38,39].
sulfonyl O atoms. Furthermore, there is also C–Hꢀ ꢀ ꢀ
p interaction
between C13A–H13A and thiazole ring (Cg1), C11A–H11A, C11A–
H11b and phenyl ring (Cg2) (Cg1 = N1, C1, C2, C7, S1; Cg2 = C2,
C3, C4, C5, C6, C7; H13Aꢀ ꢀ ꢀCg1 = 3.396, H11Aꢀ ꢀ ꢀCg2 = 3.323,
H11Bꢀ ꢀ ꢀCg2 = 3.648 Å) (Fig. 3).
The complex contains strong hydrogen bonds between oxygen
atom (O1) of carbonyl group and H atom of amine group with an
i
i
The X-ray crystallographic analysis shows that crystallographi-
cally independent Ag(I) ion is surrounded with a T-shaped geome-
try by two N atoms from o-bix ligand and one N atom from one sac
ligand. In 3, two imidazolyl arms of each o-bix ligand adopt the syn
conformation to connect two Ag(I) ions to give a compressed rect-
N1ꢀ ꢀ ꢀO1 distance of 2.924(2) Å and an N1–H1ꢀ ꢀ ꢀO1 angle of
1
56 °C ((i) x, ½ ꢁ y, ꢁ½ + z) to form the one dimensional chain
along the c axis. The most striking feature is that the complex con-
tains both intra- and inter-molecular C–Hꢀ ꢀ ꢀAg hydrogen bonding
interaction between the Ag1 ion and hydrogen atom of ethyl or
methyl groups of edmen ligand. Although regular weak hydrogen
bonding is very common, weak hydrogen bonding containing C–
Hꢀ ꢀ ꢀAg close interaction is still rare [30,40–43]. In the intramolec-
ular C2–H2Aꢀ ꢀ ꢀAg1 interaction, the Ag1ꢀ ꢀ ꢀH2A, Ag1ꢀ ꢀ ꢀC2 bond dis-
tances and C2–H2Aꢀ ꢀ ꢀAg1 angle are 2.8711(1), 3.401(2) Å and
i
angle. The corners of a rectangle are formed by N atoms (N1, N1 ,
N3 and N3 ) from o-bix ligands. The two imidazolyl moieties of
each ligand with dihedral angle of 12.42° almost overlap each
other with centroid-to-centroid distance of 3.506 Å. As shown in
i
Fig. 4, the dinuclear complex [Ag
2
2
(sac) (l
-o-bix)
2
]
2
has a chair-
-o-
bix)]. The Ag1ꢀ ꢀ ꢀAg1 distance is 3.338 Å, which is shorter than
conformation constructed by two asymmetric units [Ag(sac)(
l
5
0.0(1)°, respectively (Fig. 1). Furthermore, an intermolecular C–
i
Hꢀ ꢀ ꢀAg close interaction between Ag(I) center and the H6C atom
Fig. 4. The molecular structure of 3 with Agꢀ ꢀ ꢀAg argentophylic and face-to-face pꢀ ꢀ ꢀp stacking interactions.

O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
311
Fig. 5. Weak C–Hꢀ ꢀ ꢀp interactions in 2: (a) along a-axis, (b) along c-axis.
the sum of the van der Waals radii of Ag(I) (rvdw(Ag) = 1.72 Å) and
indicates a weak interaction between the two metal silver centers.
The C–Hꢀ ꢀ ꢀ
p interactions between the C6–H6 and imidazole
ring (Cg1) [H6ꢀ ꢀ ꢀCg1 = 2.86 Å, C6ꢀ ꢀ ꢀCg1 = 3.760 Å and C6–H6ꢀ ꢀ ꢀ
Cg1 = 164°] and C21–H21A and phenyl ring (Cg2) [H21Aꢀ ꢀ ꢀ
Cg2 = 2.99 Å, C21ꢀ ꢀ ꢀCg2 = 3.526 Å and C21–H21Aꢀ ꢀ ꢀCg2 = 116°]
play important roles in extending the 3D supramolecular frame-
work (Fig. 5). Furthermore, two adjacent imidazole rings are in-
volved in the
distance between imidazole rings 3.338 Å (Fig. 4).
p p stacking interactions with the closest centroid
ꢀ ꢀ ꢀ
The molecular structure of 4 is shown in Fig. 6. In the complex 4
the Ag1 ion is coordinated by the three nitrogen atoms from sac
and dpa ligands forming a distorted Y-shaped geometry. The dpa
ligand behaves as a bidentate ligand, forming a six-membered che-
late ring, while sac ligand is N-coordinated. The Ag–N1 bond dis-
tance of 2.122(5) Å is similar to those found in [Ag(sac)(ampy)]
(
2.107(7) Å) [28], [Ag(sac)(dmamhpy)] (2.148(1) Å), [Ag(sac)(d-
mamhpy)] (2.145(1) Å) [39], [Ag(sac)(mpr)] (2.118(1) Å) [30], but
somewhat shorter than reported for [Ag (sac) -aepy)
(2.379(3) Å) [38].
2
2
(l
2
]
(
2.449(2) Å) [28] and [Ag(sac)(dmpen)]
n
The most striking feature of the complex 4 is the presence of
N–H)ꢀ ꢀ ꢀAg close hydrogen bonding interaction between the Ag
(
ion and N–H group of dpa ligand (Fig. 7). The supramolecular com-
plexes containing (N–H)ꢀ ꢀ ꢀAg close interaction has been rarely re-
ported [45].
The Ag1ꢀ ꢀ ꢀH3 and Ag1ꢀ ꢀ ꢀN3 distances and the Ag1ꢀ ꢀ ꢀH3–N3
angle are 3.053, 3.195 Å and 91.57°, respectively [d(Agꢀ ꢀ ꢀH) ꢂ
d(Agꢀ ꢀ ꢀN)] and [Ag1ꢀ ꢀ ꢀH3–N3 < 100°]. This type interaction was
classified as being of an interaction of the pseudo-agostic (IPA)
[
18,46]. The mononuclear [Ag(sac)(dpa)] units are interconnected
through the hydrogen bonds between the N–H group of dpa ligand
Fig. 6. The molecular structure of 4 showing the atom numbering scheme.

3
12
O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
Fig. 7. (a) C@Oꢀ ꢀ ꢀp and hydrogenbonding and (b) Agꢀ ꢀ ꢀp, (N–H)ꢀ ꢀ ꢀAg and pꢀ ꢀ ꢀp interactions.
ꢁ
1
and carbonyl oxygen atoms to give an interesting hydrogen
bonded dimer (Fig. 7(a)). The adjacent dimers are connected
strong absorption band observed at 3227 cm
for
(N–H) vibration of N–H group
of edmen and dpa ligands, respectively. The broad absorption band
1 and
ꢁ1
3309 cm for 4 is attributed to the
m
though C@Oꢀ ꢀ ꢀ
p interaction between the C1–O1 and phenyl ring
ꢁ1
(
Cg1) to form a 1D supramolecular chain [Cg1 = C2–C3–C4–C5–
centered at 3387 cm is assigned to the O–H vibration of teten li-
gand. The stretching modes of the CO, SO and CNS groups have
been considered as the most important bands for characterization
of the saccharinate complexes [50]. The strong and sharp bands at
are assigned to the carbonyl
group of the sac ligand and accorded with those of N-coordinated
i
C6–C7, C@Oꢀ ꢀ ꢀCg1 = 3.735(5) Å, (i) ꢁx, ꢁy, ꢁz] (Fig. 7). The 1D
chains are further linked by Agꢀ ꢀ ꢀ interactions between the
Ag1 and C13–C15 atoms from dpa ligand to generate a 2D
layer [Agꢀ ꢀ ꢀCg13 = 3.292(6), Agꢀ ꢀ ꢀCg14 = 3.577(6), Agꢀ ꢀ ꢀCg14 =
2
p
i
i
ii
ꢁ1
1645, 1639, 1639 and 1643 cm
ii
3
1
.390(6) and Agꢀ ꢀ ꢀCg15 = 3.272(7) Å, (i): ꢁx, ꢁy, 1 ꢁ z and (ii)
ꢁ x, ꢁy, 1 ꢁ z) (Fig. 7). The Ag–C bonds distances are shorter than
monodentate sac ligand, respectively [50]. The strong bands in
ꢁ
1
the sum of the van der Waals radii of Ag and C atoms (3.42 Å) and
fall in the normal range of Agꢀ ꢀ ꢀC interactions [30,31,47,48]. Thus,
the interactions in complex 4 can be considered as a weak dihapto
aromatic coordination of the dpa ligand to the Ag(I) ions, and are
very significant for the packing of complex 4. Furthermore, there
the frequency range 1287–1301 and 1147–1152 cm for all com-
plexes correspond to the asymmetric and symmetric stretching of
the SO
2
group, respectively. The asymmetric and symmetric
absorption bands of the CNS moiety of sac in all complexes are ob-
ꢁ
1
served in the range of 1381–1334 and 961–958 cm , respectively
(Fig. S1).
are weak
p
ꢀ ꢀ ꢀ
p interactions between the pyridine rings
[
Cg1 = N2–C8–C9–C10–C11–C12; Cg2 = N4–C13–C14–C15–C16–
C17; Cg1ꢀ ꢀ ꢀCg2 = 3.803 Å]. The hydrogen bonds,
p
ꢀ ꢀ ꢀ
p
, C = Oꢀ ꢀ ꢀ
p
3
.3. Photoluminescence
and Agꢀ ꢀ ꢀC interactions cooperatively play important roles in the
formation of the resulting 2D supramolecular networks.
The emission spectra of complexes in the solid state at room
temperature are investigated; unfortunately complexes 1–3 do
not show photoluminescent properties, only complex 4 shows
emission spectrum in the room temperature (Fig. 8). In the solid
state, Na(sac) exhibits photoluminescent emission band at
339 nm (kex = 275 nm) [21]. The free dpa ligand exhibits high
3
.2. IR spectrum
Selected IR absorption bands of the complexes 1–4 are pre-
sented in Table 1, together with the IR data of [Ag(sac)] [49]. The

O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
313
3
63
432
3
00
350
400
450
500
550
Wavelength (nm)
Fig. 8. Solid-state emission spectra of complex 4 (ꢀ ꢀ ꢀ) and dpa ligand (—).
emission at 363 nm upon excitation at 284 nm, attributed to the
501 and 587 °C (found 80.37, calcd. 80.58%). The final decomposi-
tion product is metallic silver.
⁄
p
?
p
intraligand transitions. The weakly emission band is ob-
served at 432 nm for complex 4, when excited at 361 nm. Com-
pared to the photoluminescence spectrum of dpa ligand, the
emission of 4 shows red-shift of 69 nm emission. The coordination
of the ligand to the Ag(I) ion plays an important role in the red shift
of the emission [51–54].
3
.4.4. [Ag(sac)(dpa)] (4)
The thermal decomposition pathway of 4 was followed up to
7
00 °C in a static atmosphere of air (Fig. S5). The complex 4 is sta-
ble up to 223 °C and then begins to decompose with melting at
24 °C. The first decomposition stage between 225 and 387 °C cor-
2
3.4. Thermal analyses
responds to the endothermic removal of dpa ligand with a mass
loss of 38.38% (calcd. 37.12%). Decomposition of sac begins at
The thermal decomposition processes of the complexes 1–4
were followed up to 700 °C in a static atmosphere of air.
3
87 °C and ends at 573 °C with mass loss of 37.74% (calcd.
3
9.49%), giving a final decomposition product of metallic silver (to-
tal mass loss: found 76.12% and calcd. 76.61%).
3.4.1. [Ag(sac)(edmen)] (1)
The complex 1 is thermally stable up to about 130 °C and it be-
gins to decompose after melting at 119 °C (Fig. S2). It is difficult to
distinguish the decomposition stage because of a continuous
weight loss as observed. Therefore, it is impossible to calculate
the mass loss of each step. TG curve of 1 shows the mass loss of
4. Conclusions
In this work, we synthesized and characterized four new Ag(I)
saccharinate complexes with N-donor edmen, teten, o-bix and
7
4.20% (calcd. 73.45%) in the range 125–395 °C, corresponding to
the exothermic and endothermic release of edmen (DTAmax
87 °C) and sac (DTA = 281 °C) ligands, respectively. The two
2
dpa ligands. The steric and electronic effects of CH or OH substit-
=
uents of N-donor ligands lead to C–Hꢀ ꢀ ꢀAg interactions and regu-
late the supramoleculer structures of resultant coordination
compounds. Spectral and thermal analysis data for the complexes
are in agreement with the crystal structures. The photolumines-
cence spectrum shows that complex 4 displays red-shift fluores-
cent emission in the solid state at room temperature.
1
exothermic peaks at 463 and 577 °C are attributed to the burn of
remaining organic part. The final decomposition product is the
metallic silver.
3.4.2. [Ag(sac)(teten)] (2)
The complex [Ag(sac)(teten)] is stable up to 168 °C (Fig. S3). It
begins to decompose with melting at 169 °C. The weight loss of
4.23% (calcd. 44.90%) between 170 and 424 °C is attributed to
the loss of teten ligand. In the following stage, the strong exother-
mic mass loss processes occur in the temperature range of 424–
03 °C. During this stage, the remaining organic residue is burnt
DTAmax = 580 °C). The final solid product of the thermal decompo-
sition was identified as metallic silver (found 79.81, calcd. 79.51%).
Acknowledgments
4
We thank Dr. Ertan Sß ahin of Ataturk University, Dr. Filiz Yılmaz
of Anadolu University and Dr. Murat TA Sß of Giresun University for
the X-ray diffraction analyses.
6
(
Appendix A. Supplementary data
3
.4.3. [Ag
The [Ag
Fig. S4). Its decomposition begins at 297 °C after melting at 217
and 236 °C. The two endothermic peaks of 3 (DTAmax = 347 and
53 °C) between 297 and 396 °C, correspond to the release of the
2
(sac)
2
(o-bix)
2
] (3)
CCDC 851680, 851681, 851682 and 866493 contain the supple-
mentary crystallographic data for 1, 2, 3 and 4, respectively. These
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)
1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary
data associated with this article can be found, in the online version,
at http://dx.doi.org/10.1016/j.poly.2012.05.034.
2
(sac)
2
(o-bix)
2
] (3) complex has a high thermal stability
(
3
o-bix ligands (found 46.84, calcd. 45.10%). In the following stages
in the temperature range 396–603 °C, the decomposition of the
sac ligand occurs with two violently exothermic DTA peaks at

3
14
O.Z. Ye ßs ilel et al. / Polyhedron 42 (2012) 307–314
[
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