Novel silver(I)-saccharinate complexes exhibiting Ag·· ·π and C-H···Ag close interactions with a new coordination mode of saccharinate

Article abstract of DOI:10.1016/j.poly.2010.11.001

Two novel silver(I) complexes, namely [Ag₂(μ₃-sac) ₂(μ-nmpen)]_n (1) and [Ag(sac)(mpr)]₂ (2) (sac = saccharinate; nmpen = N-methyl-1,3-propanediamine; mpr = 2-methyl-1-pyrroline) have been synthesized and characterized by IR spectra, thermal (TG, DTG and DTA) analysis and single crystal X-ray diffraction techniques. Complexes crystallize in the monoclinic system with the space group C2/c and P2₁/c, respectively. In 1, Ag(I) ion exhibits a distorted tetrahedral geometry by tridentate μ₃-bridging sac and μ₂-bridging nmpen ligands. The sac ligand exhibits a new μ₃-coordination mode by means of μ₂-bridging O atom of sulfonyl group and N atom of imino group. Furthermore, complex 1 exhibits a two-dimensional polynuclear structure. In 2, the silver(I) ion is linearly coordinated by the N atoms of a sac and a mpr ligands, forming mononuclear species. The individual molecules are linked into dimers by Ag·· ·C_sac (η¹) interactions between silver(I) ion and phenyl ring of the adjacent complex and these dimers are assembled into two-dimensional layered networks through weak Ag···Ag (3.507 ), SO···Ag (2.961 ) and π··· π interactions. The most interesting structural features of complexes is the presence of obvious C-H···M hydrogen-bonding interactions between the Ag centers and H atoms of nmpen or mpr ligands.

Full text of DOI:10.1016/j.poly.2010.11.001

Polyhedron 30 (2011) 364–371
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Novel silver(I)–saccharinate complexes exhibiting Agꢀꢀꢀ
p
and C–HꢀꢀꢀAg close
interactions with a new coordination mode of saccharinate
a,
⇑
a
b
Okan Zafer Ye ßs ilel , Güne ßs Günay , Orhan Büyükgüngör
a
Department of Chemistry, Faculty of Arts and Sciences, Eski ßs ehir Osmangazi University, 26480 Eski ßs ehir, Turkey
Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Kurupelit, Samsun, Turkey
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 26 July 2010
Accepted 1 November 2010
Available online 16 November 2010
Two novel silver(I) complexes, namely [Ag2(l3-sac)2(l-nmpen)]n (1) and [Ag(sac)(mpr)]2 (2) (sac = sac-
charinate; nmpen = N-methyl-1,3-propanediamine; mpr = 2-methyl-1-pyrroline) have been synthesized
and characterized by IR spectra, thermal (TG, DTG and DTA) analysis and single crystal X-ray diffraction
techniques. Complexes crystallize in the monoclinic system with the space group C2/c and P2
tively. In 1, Ag(I) ion exhibits a distorted tetrahedral geometry by tridentate -bridging sac and
ing nmpen ligands. The sac ligand exhibits a new -coordination mode by means of -bridging O atom
1
/c, respec-
l
3
l -bridg-
2
Keywords:
l
3
l
2
Saccharinate complexes
Silver(I) complexes
AgꢀꢀꢀC interaction
C–HꢀꢀꢀAg interaction
of sulfonyl group and N atom of imino group. Furthermore, complex 1 exhibits a two-dimensional poly-
nuclear structure. In 2, the silver(I) ion is linearly coordinated by the N atoms of a sac and a mpr ligands,
1
forming mononuclear species. The individual molecules are linked into dimers by AgꢀꢀꢀCsac
(
g
) interac-
tions between silver(I) ion and phenyl ring of the adjacent complex and these dimers are assembled into
two-dimensional layered networks through weak AgꢀꢀꢀAg (3.507 Å), S@OꢀꢀꢀAg (2.961 Å) and
p p
ꢀꢀꢀ
interac-
tions. The most interesting structural features of complexes is the presence of obvious C–HꢀꢀꢀM hydrogen-
bonding interactions between the Ag centers and H atoms of nmpen or mpr ligands.
Ó 2010 Elsevier Ltd. All rights reserved.
1
. Introduction
Supramolecular chemistry generally encompasses the chemis-
[16,17], bis(monodentate) [18,19], bidentate (N, O) and bridging
forming [20,21] (Scheme 1). Chemistry of metal–saccharin com-
plexes is an interesting area of research because of the potential
biological significance of such compounds [22]. The structural
properties of saccharin salts and complexes with various metals
have been intensively investigated during the last few decades
[21,23–46]. Synthesis, structural and thermal characterization of
silver(I) complexes of with mono- and bidentate N-donor ligands
such as 1,2-bis[1-(pyridin-2-yl)ethylidene]hydrazine] [28], aceto-
try of molecular recognition and self-assembly [1], which mainly
based on the non-covalent bonds such as metal coordination,
hydrogen bonds,
pꢀꢀꢀ
p
stacking, C–Hꢀꢀꢀ
p and van der Waals interac-
tions [2,3]. Hydrogen bonding interactions, being reasonably strong
and highly directional, are widely used as structure-directing tools
in supramolecular assembly to generate new topological structures.
The most controversial and discussed weak hydrogen bond donors
is the C–H group [4], which contains C–HꢀꢀꢀX (X is electronically
negative atom such as O, N or F) weak interactions. The use of
C–HꢀꢀꢀX interactions in construction of new topological structures
has attracted much attention [5], while researches on the usage of
0
nitryl [47], pyrazine [48], piperazine and N,N -bis(2-hydroxyethyl)
piperazine [49], pyridazine [50], pyrazole, imidazole [51], 2-meth-
ylpyrazine, pyrazine-2-carboxamide [52], ethylenediamine deriva-
tive [34,53], 2-pyridylmethanol, 2,6-pyridinedimethanol [23–25]
appear in recent literature. Up to now, although the literature lists
many reports on the coordinating modes of sac ligand (Scheme 1),
the binding in complex 1 is not known. As it is well known, silver(I)
ion is a soft acid and coordinates to soft bases such as S- and N-con-
taining ligands therefore a favorable building block for coordina-
tion polymers [54,55], since it exhibits linear, bent, trigonal
planar, T-shaped, tetrahedral, trigonal pyramidal coordination
with different ligands [56–58]. Moreover, Ag(I) ion is apt to form
short AgꢀꢀꢀAg contacts as well as ligand unsupported interaction
which has been proved to be two of the most important factors
contributing to the formation of such complexes and special
properties [47].
C–HꢀꢀꢀAg and C–Hꢀꢀꢀ
p interactions are relatively rare [6–11].
Saccharin (o-sulfobenzimide) and its salts have been used as an
artificial sweetener in vitamins, pharmaceuticals and in such prod-
ucts as jams and candy [12,13]. It is well known that saccharinate
acts as a polyfunctional ligand in metal complexes and coordinates
to metals by means of its carbonyl oxygen, two sulfonyl oxygen
atoms and a nitrogen atom, exhibiting different coordination
modes such as as monodentate-N [14,15] and monodentate-O
⇑
Corresponding author.
E-mail address: yesilel@ogu.edu.tr (O.Z. Ye sß ilel).
0
277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.11.001

O.Z. Ye ßs ilel et al. / Polyhedron 30 (2011) 364–371
365
O
O
O
C
C
N
S
C
N
H
N
M
S
S
O
O
O
O
O
O
I
II
(
NH
4
, Na, K, Rb, Cs, Be, Mg,
Ca, Sr, Ba)
Saccharin
(M = V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ag, Pt, Pd, Au, Hg)
O
C
M
O
O
M
M
C
C
N
N
S
N
M
S
S
O
O
O
O
O
O
III
IV
V
(
M = V, Ni, Cu, Co, Zn, Cd,
(M = Cr, Pb, Ag, Cd, Cu)
(M = Ba, Pb, Ag, Hg, Cr, Cu)
Gd,Lu)
O
C
M
M
O
O
C
M
N
M
C
N
M
S
N
S
S
O
O
O
O
M
M
O
O
VI
VII
VII
(
M = Cr, Pb, Ag, Ba, Cd, Cu,
(
M = Cr, Pb, Ag, Ba, Cd, Cu)
Hg)
(M = Cr, Pb, Ag, Ba, Cd, Cu)
O
C
O
O
M
C
N
M
N
N
M
S
S
S
M
O
O
O
O
O
O
M
M
M
M
X
IX
M = Cr, Pb, Ag, Ba)
(M = Cr, Pb, Ag, Tl)
XI*
(M = Ag) this study
(
Scheme 1. Coordination modes of the saccharinate ligand (* a new coordination mode).
In the present paper, we describe the synthesis, IR spectra and
thermal properties and structural characterization of two new sil-
ver(I)–saccharinate complexes with N-methyl-1,3-propanediamine
recorded using a Perkin–Elmer 100 FT-IR spectrometer with KBr
ꢁ
1
discs (4000–400 cm ). Thermogravimetric data were obtained
on a Diamond TG/DTA thermal analyzer in the static air atmo-
ꢁ1
(
nmpen), [Ag
2
(l -sac)
3
2
(l
-nmpen)]
n
(1) and 2-methyl-1-pyrroline
sphere with a heating rate of 10 K min in the temperature range
(
mpr), [Ag(sac)(mpr)]
2
(2) and present the C–HꢀꢀꢀAg close interac-
30–700 °C using platinum crucibles.
tions, for the first time, in a silver(I)–sac complex.
2 3 2 n 2
2.2. Synthesis of [Ag (l -sac) (l-nmpen)] and [Ag(sac)(mpr)]
2
. Experimental
Na(sac)ꢀ15/8H
2
O [39] (0.25 g, 1.22 mmol) was added to an
(0.207 g, 1.22 mmol) with stir-
2.1. General
aqueous solution (30 mL) of AgNO
3
ring at room temperature. Then, a suspension with a white precip-
itate formed and the addition of nmpen (0.090 g, 1.22 mmol) to the
suspension resulted in a clear solution, which was kept in darkness
All chemicals were reagent grade, purchased from commercial
sources and used without further purification.IR spectra were

3
66
O.Z. Ye ßs ilel et al. / Polyhedron 30 (2011) 364–371
at room temperature. The colorless single crystals of 1 obtained in
two weeks also they were filtered and washed with 5 mL of etha-
nol and dried in air.
used to prepare material for publication: WINGX [62]. A summary
of the crystallographic data is given in Table 1.
The preparative method is similar to that for compound 2, using
mpr ligand (0.101 g, 1.22 mmol) instead of nmpen.
3
. Results and discussion
3
3
.1. Crystal structures
2.3. X-ray structure determination
2 3 2 n
.1.1. [Ag (l -sac) (l-nmpen)]
A view of the molecular structure of complex 1 is shown in
Diffraction experiments were carried out at 296 K on a Stoe
Fig. 1, together with the atom numbering scheme. Selected bond
distances and angles are listed in Table 2. Single X-ray crystal
analysis reveals that the complex 1 crystallizes in monoclinic
space group C2/c, which is a two-dimensional coordination poly-
mer. The asymmetric unit of the complex 1 contains a half of the
molecule and it has 2-fold symmetry, with atom C10 sitting on
the 2-fold axis. Therefore, the occupation factor of the methyl
group of nmpen was fixed to 0.5. The sac ligand acts as a triden-
tate bridging ligand between three Ag(I) centers through the imi-
IPDS diffractometer. The structures were solved by direct methods
and refined using the programs SHELXS97 and SHELXL97 [59]. All
non-hydrogen atoms were refined anisotropically by full-matrix
least-squares methods [59]. The hydrogen atoms were placed in
geometrically idealized positions and refined as riding atoms. Data
collection: X-AREA, cell refinement: X-AREA, data reduction: X-RED [60];
program(s) used for molecular graphics: MERCURY [61]; software
no N and sulfonyl
l-O atoms, forming one-dimensional linear
Table 1
Crystallographic data and structure refinement parameters for complexes.
chain. In addition to the most observed coordination modes,
the sac ligand exhibits a new coordination mode. Four-mem-
Complex
1
2
2 2
bered bimetallic ring, Ag O core, is also formed by two silver(I)
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
18
2
H20Ag N
4
O
S
6 2
C
12
H
13AgN
2
O
3
S
i
ions linked by two sulfonyl oxygen bridges. The Ag1ꢀꢀꢀAg1 dis-
tance (4.233(2) Å, ((i) 1 ꢁ x, ꢁy, 1 ꢁ z)) is greater than the sum
of the van der Waals radii of two silver(I) atoms (3.44 Å) and,
thus AgꢀꢀꢀAg interaction is not found. As shown in Fig. 2, the N
atoms of nmpen ligand act as a bridge to link 1D chains into a
668.24
monoclinic
C2/c
21.9040 (10)
5.2345 (2)
19.6649 (9)
96.344 (4)
2240.90 (17)
4
1.98
1.981
0.49 ꢂ 0.22 ꢂ 0.05
1.87–26.50
11 969
373.17
monoclinic
P2 /c
15.0330 (8)
11.7707 (4)
20.6774 (10)
131.347 (3)
2746.8 (2)
8
1.62
1.805
0.27 ꢂ 0.15 ꢂ 0.08
1.80–28.06
20 018
1
b (Å)
c (Å)
2
D coordination polymer. There are only a few examples for
b (ꢀ)
V (Å )
3
the nmpen ligand acting as a bridge between the Ag atoms,
forming a two-dimensional coordination polymer as shown in
Fig. 2. Each Ag(I) ion is coordinated by two N atoms (N1 and
N2) of sac and nmpen ligands, two sulfonyl oxygen atoms (O3
Z
l
D
(mm 1
ꢁ
)
calc (Mg mꢁ3)
Crystal size (mm)
h Range (°)
Measured reflections
i
and O3 ) of two different sac ligands, showing a slightly distorted
tetrahedral geometry.
Independent reflections
2332
0.049
0.041, 0.110
1.07
0.88, ꢁ0.66
5688
0.041
0.052, 0.134
0.98
2.67, ꢁ1.18
The bond length of Ag1–N1 (2.130(3) Å) is shorter than the cor-
R
R
(int)
responding bond in [Ag
sac)(ppz)] (2.172(3) Å) [63] and [Ag
[31]. However, this bond distance is similar to the corresponding
values found in reported [Ag (sac) (mpyz) (H O)] (2.133(3) Å)
2
(sac)
2
(pyzca)
2
] (2.154(2) Å) [52], [Ag(
l-
1
, wR
n
2 2
(sac) (l-aepy)] (2.449(2) Å)
2
Goodness-of-fit on F
ꢁ
3
D
q
max
,
D
q
min (e Å
)
4
4
2
2
Fig. 1. Molecular structure of 1 with atom-labeling scheme (some hydrogen atoms are omitted for clarity, symmetry codes: (i) 1 ꢁ x, y, 1.5 ꢁ z; (ii) 1 ꢁ x, ꢁ1 + y, 1.5 ꢁ z;
iii) x, 1 ꢁ y, ½ + z; (iv) x, ꢁ1 + y, z; (v) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z; (vi) x, 1 + y, z; (vii) 1 ꢁ x, 1 + y, 1.5 ꢁ z).
(

O.Z. Ye ßs ilel et al. / Polyhedron 30 (2011) 364–371
367
[
52], [Ag(sac)(Ph
2
SNH)] (2.085(2) Å) [64]. The sulfonyl oxygen
Table 2
i
Selected geometric parameters and hydrogen bond geometry for complexes.
atom is weakly coordinated to the Ag atom (Ag1–O1 = 2.669(4)
ii
and Ag1–O1 = 2.687(4) Å, (i) x, y ꢁ 1, z, (ii) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z).
Bond lengths (Å) and angles (°)
These bond distances are shorter than those reported [Ag(sac)(dm-
py)] (2.822(1) and 2.938(1) Å)[32], but are similar to the corre-
1
2
Ag1–N1
Ag1–N2
Ag1-O1
Ag1-O1
2.130 (4)
2.205 (5)
2.669(4)
2.687(4)
162.3 (2)
Ag1–N1
Ag1–N2
Ag2–N3
Ag2–N4
N1–Ag1–N2
N3–Ag2–N4
2.118 (4)
sponding values found in the [Ag
and Na[Ag(sac) ] (2.640(1) Å) [66] (Table 2).
The crystal packing of complex is stabilized through intra- and
inter-molecular weak C–HꢀꢀꢀAg, hydrogen bonding, C@Oꢀꢀꢀ
C@OꢀꢀꢀAg and S@OꢀꢀꢀAg interactions, resulting in a 3D framework
Fig. 3). It is worth noting that one of the interesting structural fea-
2 2 2
(sac) (pyet) ] (2.645(1) Å) [65]
2.129 (4)
2.093 (5)
2.101 (5)
165.3 (2)
171.0 (2)
i
2
ii
N1–Ag1–N2
p,
Hydrogen bond geometry for 1
(
D–HꢀꢀꢀA
HꢀꢀꢀA
DꢀꢀꢀA
D–HꢀꢀꢀA
tures of complex 1 is the presence of C–HꢀꢀꢀAg close interactions
between the Ag centers and some nmpen H atoms identified by
X-ray diffraction. The AgꢀꢀꢀH distances of 2.684, 2.931 Å, AgꢀꢀꢀC dis-
tances of 3.275, 3.765 Å and C–HꢀꢀꢀAg angles of 119.71°, 144.79° are
similar to those values for reported Ag(I) complexes [10,11]. This
interactions should be well described as being of a weak inter-
molecular C–HꢀꢀꢀAg hydrogen bonding. To the best of our knowl-
edge, this manner has not been reported so far although there
are many complexes of sac ligand [28,29,34,47,52]. Besides, the
i
N2–H2BꢀꢀꢀO2
2.213 (3)
3.035 (5)
155.3 (3)
Symmetry code: (i) ꢁx + 1, 1ꢁy, ꢁz + 1, (ii) x, ꢁ1 + y, z.
3.1.2. [Ag(sac)(mpr)]
2
The molecular structure of 2 with the atom labelling is shown in
Fig. 4. The selected bond lengths and angles and hydrogen bonding
geometry are given in Table 2. The complex 2 crystallizes in the
1
monoclinic space group P2 /c. The large residual electron density
peak (2.67 e Å ) is situated 0.97 Å from Ag2. The asymmetric unit
of 2 is composed of two crystallographic independent [Ag(sac)
complex also contains intra-network C@Oꢀꢀꢀ
p
supramolecular
3
i
interactions between the C7@O3 and phenyl ring (C7@O3ꢀꢀꢀCg2 =
i
3
.719 Å, (i): x, ꢁ1 + y, z]. Moreover, N2–H2BꢀꢀꢀO2 hydrogen bonds
(
mpr)] complex. Each silver(I) ion is coordinated by a sac and a
with an N2ꢀꢀꢀO2 distance of 3.035 (5) Å, C@OꢀꢀꢀAg and S@OꢀꢀꢀAg
interactions play an important role in stabilizing the 3D
framework.
mpr ligands, forming a slightly distorted linear AgN motif with
an N1–Ag1–N2 and N3–Ag2–N4 angles of 165.3(2) and 171.0(2)°,
respectively. The Ag1–N1 and Ag2–N3 bond distances of 2.130
2
Fig. 2. A view of the two-dimensional framework in 1 (all hydrogen atoms are omitted for clarity).

3
68
O.Z. Ye ßs ilel et al. / Polyhedron 30 (2011) 364–371
Table 3
(2) Å) [67] complexes, but significantly shorter than the corre-
sponding distances reported Ag–sac complexes [38,45].
Assignment of the most characteristic IR bands of 1 and 2.
*
Assignments
Complexes
The shortest AgꢀꢀꢀAg distance between complexes is 3.507 Å,
which is slightly longer than twice the van der Waals radii of
Ag(I) (3.44 Å), indicating a weak interaction between the Ag(I) ions.
The sac and mpr ligands are essentially planar and the dihedral an-
gles between the mean planes of the sac and mpr rings are 14.04
and 14.81°. In 2, the Ag1 ion is linear coordination sphere which
1
2
m(NH
2
)/(NH)
3344/3280s
3072vw
–
m(CH)/(CH
2
)
3086vw
2825vw
1665vs
1588s
1329m
962s
2
872vw
m
m
m
m
m
m
(C@O)
(C–C)
1640–1626vs
1583s
1337m
968s
1152vs
1253vs
i
is extended to three (2 + 1) by the sulfonyl O2 atom [Ag1–O2 =
s
(CNS)
asym(CNS)
(SO
2
.961 Å; (i): x, ꢁ1 + y, z] and, therefore in the dinuclear unit, Ag1
ion is three coordinated, exhibiting a distorted ‘‘T’’ shaped AgN
2
O
s
2
)
1148vs
1282vs
asym(SO
2
)
coordination. Furthermore, we surprisingly found the existence
of the closest contacts between silver ion (Ag1 and Ag2) and phe-
nyl ring which is associated with the C2, C3, C4, C7, C12, C13, C17,
C18 and C19 atoms (Fig. 5). The Ag–C bond distances in range from
*
ꢁ1
Frequencies in cm , m = medium; vw = very weak; vs = very strong; s = strong.
3
.249 to 3.807 Å, which are all within the normal range generally
(
[
4) and 2.093 (5) Å is also similar to those found in reported for
Ag(sac)(Ph SNH)] (2.085(2) Å) [64] and [Ag(sac)(apy)] (2.103
2
found in the literature [34,47]. The Ag1–C18 (3.249 Å) and Ag2–
C3 (3.283 Å) are obviously shorter than the sum of the van der
Fig. 3. The intra- and inter-molecular C-HꢀꢀꢀAg, C@OꢀꢀꢀAg and S@OꢀꢀꢀAg interactions in 1 (some hydrogen atoms and phenyl group of sac ligand are omitted for clarity).
Fig. 4. The molecular structure of 2, showing the intra- and inter-molecular C–HꢀꢀꢀAg, pꢀꢀꢀp and AgꢀꢀꢀC interactions.

O.Z. Ye ßs ilel et al. / Polyhedron 30 (2011) 364–371
369
Waals radii of Ag and C (3.42 Å) [47]. These interactions in 2 may
be considered as a medium monohapto aromatic coordination of
the phenyl ring of sac to the Ag(I) ions, and are very significant,
in the present case, for the packing of 2 in the solid state. Although
these interactions have been widely observed, such interactions
involving sac ligand in the solid state have rarely been documented
in the literatures [29,34,47]. In addition, there are inter-molecular
C24–H24BꢀꢀꢀAg2 angles of 120.48 and 118.71°. These values are
similar to those values for reported Ag(I) complexes and therefore,
such C–HꢀꢀꢀM close interaction mentions as a weak intramolecular
hydrogen bonding [8,10].
3.2. IR spectra
face to face
p
ꢀꢀꢀ
p
stacking interactions between the phenyl and pyr-
The frequencies of most significant bands in the spectra of the
complexes are shown in Table 3. The position of bands in the spec-
tra of the complexes is similar to one another. IR spectra of the sil-
oline rings of adjacent complex with a centroid–centroid separa-
tion of 3.914 and 3.8587 Å. To the best of our knowledge, these
distances are similar to those values for reported Ag(I)–sac com-
plexes (Fig. 5) [32,64].
There are also C–HꢀꢀꢀAg1 close intramolecular interactions be-
tween silver ions (Ag1 and Ag2) centers and H atoms (H12A and
H24B) atoms of methyl group of mpr ligand, with Ag1ꢀꢀꢀH12A
and Ag2ꢀꢀꢀH24B distances of 2.814 and 2.727 Å, Ag1ꢀꢀꢀC12 and
Ag2ꢀꢀꢀC24 the distances of 3.404 and 3.297 Å and C12–H12AꢀꢀꢀAg1,
ver(I) complexes exhibit characteristic features of NH/NH , CO, CC
2
symmetric and antisymmetric SO . The strong bands in the 3340–
2
ꢁ1
3280 cm region could be attributed to the
2
m(NH/NH ) stretching
vibrations of nmpen ligand. The relatively weak bands at around
ꢁ1
3072–2872 cm are due to absorption of CH group vibrations con-
taining the ring H atoms. The (C@O) bands of sac ligands clearly
are separate as doublets at 1640 and 1626 cm , indicating the
m
ꢁ1
Fig. 5. The inter-molecular AgꢀꢀꢀC/N/S, AgꢀꢀꢀAg, C@OꢀꢀꢀAg, S@OꢀꢀꢀAg and pꢀꢀꢀp interactions (hydrogen atoms are omitted for clarity).
Fig. 6. TG, DTG and DTA curves of 1.

3
70
O.Z. Ye ßs ilel et al. / Polyhedron 30 (2011) 364–371
different interactions of sac ligand in complex 1 and for 2 appears
[5] D. Kumar, A. Ballabh, D. Jose, P. Dastidar, A. Das, Cryst. Growth Des. 5 (2005)
651.
ꢁ1
as strong band at 1665 cm . For complex 1 and 2, the absorption
[
[
6] J. Fan, C. Slebodnick, D. Troya, R. Angel, B. Hanson, Inorg. Chem 44 (2005) 2719.
7] M. Castro, J. Cruz, H. Lopez-Sandoval, N. Barba-Behrens, Chem. Commun.
(2005) 3779.
–1
bands with strong intensity around 1583 and 1588 cm corre-
spond to (CC) vibrations of the aromatic phenyl ring. In the IR
spectra of complex 1, the characteristic bands of SO
m
[
[
8] T.S. Thakur, G.R. Desiraju, Chem. Commun. (2006) 552.
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2
groups occur
ꢁ1
ꢁ1
at 1253 cm for antisymmetric stretching, and at 1152 cm for
the symmetric stretching. In contrast, the corresponding absorp-
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ꢁ
1
tion bands for 2 observed at about 1282 and 1148 cm . Additional
[
11] D. Braga, F. Grepioni, E. Tedesco, K. Biradha, G.R. Desiraju, Organometallics 16
1997) 1846.
ꢁ
1
ꢁ1
peaks at 1337 and 968 cm for 1, 1329 and 962 cm for 2 are
attributed to the symmetric and antisymmetric stretching modes
of the CNS moiety of sac ligands, respectively.
(
[12] D.J. Ager, D.P. Pantaleone, S.A. Henderson, A.R. Katritzky, I. Prakash, D.E.
Walters, Angew. Chem., Int. Ed. 37 (1998) 1803.
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Chim. Acta 72 (1983) 21.
[
[
Vibrations related to the Ag–N and Ag–O vibrations could not be
ꢁ1
identified for certain. Also, the weak bands below 600 cm may be
attributed to both Ag–N and Ag–O vibrations.
[
16] O.V. Quinzani, S. Tarulli, C. Marcos, S.G. Granda, E.J. Baran, Z. Anorg. Allg. Chem.
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6
3
3
.3. Thermal properties
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Fun, S. Ng, Z. Anorg. Allg. Chem 628 (2002) 2930.
[
[
18] N. Alfaro, F. Cotton, L. Daniels, C. Murillo, Inorg. Chem. 31 (1992) 2718.
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190 (1991) 89.
2 3 2 n
.3.1. [Ag (l -sac) (l-nmpen)]
Complex 1 shows three stages decomposition process (Fig. 6). In
[
[
[
20] R. Weber, M. Gilles, G. Bergerhoff, Z. Kristallogr. 206 (1993) 273.
21] E.J. Baran, V.T. Yilmaz, Coord. Chem. Rev. 250 (2006) 1980.
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the first stage, complex starts to lose nmpen ligand between 200
and 373 °C with an experimental mass loss of 12.52% (calcd. mass
loss 13.19%). The second stage is related to the degradation of two
sac ligands by giving endothermic effect (found = 52.45,
calcd. = 52.52%). In the last stage (which is the temperature be-
tween 590 and 700 °C) is extremely exothermic, sac ligand is
abruptly burnt (DTA = 673 °C). The total mass loss of all decompo-
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[
[
24] E.J. Baran, C.C. Wagner, M. Rossi, F. Caruso, Z. Anorg. Allg. Chem. 627 (2001) 85.
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(
2002) 657.
[26] E.G. Ferrer, S.B. Etcheverry, E.J. Baran, Monatsh. Chem. 124 (1993) 355.
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[
[
28] E. Guney, V.T. Yilmaz, O. Buyukgungor, Polyhedron 29 (2010) 1437.
29] E. Guney, V.T. Yilmaz, O. Buyukgungor, Inorg. Chem. Commun. 13 (2010)
sition process is 67.71% (calcd. 68.91%) and suggests that Ag
the end product.
2
O is
5
63.
30] E. Guney, V.T. Yilmaz, A. Sengul, O. Buyukgungor, Inorg. Chim. Acta 363 (2010)
38.
31] S. Hamamci, V.T. Yilmaz, W.T.A. Harrison, Z. Naturforsch. B 60 (2005) 978.
[
[
4
3
.3.2. [Ag(sac)(mpr)]
2
Complex 2 shows two stages decomposition process and stable
up to 118 °C. In the first stage, the complex starts to lose mpr li-
gand and decompose groups of sac ligand between 118 and
15 °C with an experimental mass loss of 52.68%. The second stage
is related to the degradation of the rest sac ligand moiety by giving
exothermic effect and sac ligand is abruptly burnt (DTA-
max = 603 °C). The total mass loss of all decomposition process is
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23.
4
[
33] H. Icbudak, H. Olmez, O.Z. Yesilel, F. Arslan, P. Naumov, G. Jovanovski, A.R.
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3
[
[
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4178.
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35 (1998) 579.
7
7.26% and suggests that metallic Ag is the end product.
[36] P. Naumov, G. Jovanovski, Acta Chim. Slov. 46 (1999) 389.
[
[
37] P. Naumov, G. Jovanovski, Spectrosc. Lett. 32 (1999) 237.
38] P. Naumov, G. Jovanovski, S. Abbrent, L.E. Tergenius, Thermochim. Acta 359
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4
. Conclusion
[
39] P. Naumov, G. Jovanovski, O. Grupce, B. Kaitner, A.D. Rae, S.W. Ng, Angew.
Chem., Int. Ed. 44 (2005) 1251.
In conclusion, two novel Ag(I) complexes, [Ag
2
(l
3
-sac)
2
(l
-
[40] P. Naumov, G. Jovanovski, M. Ristova, I.A. Razak, S. Cakir, S. Chantrapromma,
H.K. Fun, S.W. Ng, Z. Anorg. Allg. Chem. 628 (2002) 2930.
nmpen)] (1) and [Ag(sac)(mpr)] , have been synthesized and char-
n
2
[
[
41] P. Naumov, G. Jovanovski, K. Sakurai, Cryst. Growth Des. 6 (2006) 815.
42] P. Naumov, G. Jovanovski, S. Tanceva, S.W. Ng, Z. Anorg. Allg. Chem. 632 (2006)
acterized. The complexes 1 and 2 exhibit rare C–HꢀꢀꢀAg hydrogen
bonding interactions. Furthermore, it appears that the complex 2
454.
1
involved the AgꢀꢀꢀC (
g
) interactions between the Ag atoms and
[43] P. Naumov, G. Jovanovski, A. Todorovska, J. Mol. Struct. 563 (2001) 341.
[
[
44] P. Naumov, G. Jovanovski, A. Todorovska, Spectrochim. Acta A 58 (2002) 1903.
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phenyl groups of sac ligand. In addition, a new coordination mode
of the sac ligand is observed in 1. These complexes exhibit a three-
dimensional (3D) framework based on
AgꢀꢀꢀCsac and C–HꢀꢀꢀAg interactions.
pꢀꢀꢀ
p, C–Oꢀꢀꢀ
p, C–Hꢀꢀꢀ
p,
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[
[
47] V.T. Yilmaz, S. Hamamci, C. Kazak, J. Organomet. Chem. 693 (2008) 3885.
48] S. Hamamci, V.T. Yilmaz, S. Gumus, O. Bueyuekguengoer, J. Struct. Chem. 19
(
2008) 123.
[
[
[
49] V.T. Yilmaz, E. Senel, C. Kazak, Polyhedron 26 (2007) 3199.
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51] V.T. Yilmaz, V. Kars, C. Kazak, Z. Naturforsch. B 61 (2006) 555.
Appendix A. Supplementary material
CCDC 728983 and 728984 contains the supplementary crystal-
lographic data for 1 and 2. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/datarequest/cif.
[52] V.T. Yilmaz, E. Senel, E. Guney, C. Kazak, Inorg. Chem. Commun. 11 (2008)
330.
1
[
53] O.Z. Yesilel, G. Kastas, C. Darcan, I. Ilker, H. Pasaoglu, O. Buyukgungor, Inorg.
Chim. Acta 363 (2010) 1849.
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