Syntheses, thermal analyses, crystal structures and antimicrobial properties of silver(I)-saccharinate complexes with diverse diamine ligands

Article abstract of DOI:10.1016/j.ica.2010.02.013

Five new silver(I)-saccharinate complexes [Ag₂(sac)₂(tmen)₂] (1), [Ag₂(sac)₂(deten)₂] (2), [Ag₂(sac)₂(dmen)₂] (3), [Ag(sac)(N,N-eten)] (4), and [Ag(sac)(dmpen)]_n (5); (sac = saccharinate, tmen = N,N,N′,N′-tetramethylethylenediamine, deten = N,N′-diethylethylenediamine, dmen = N,N′-dimethylethylenediamine, N,N-eten = N,N-diethylethylenediamine and dmpen = 1,3-diamino-2,2-dimethylpropan) have been synthesized and characterized by elemental analyses, IR, thermal analyses, single crystal X-ray diffraction and antimicrobial activities. The crystallographic analyses show that all the complexes crystallize in monoclinic space group P2₁/c. In 1, the sac ligand acts as a bridge to connect the silver centres through its imino N and carbonyl O atoms forming an eight-membered bimetallic ring in a chair conformation. Complex 2 has also a dimeric structure in which the monomeric [Ag(sac)(deten)] units are linked by Ag?Ag interactions. In 3, saccharinate ligand acts as a bridging bidentate ligand between two silver(I) centres through sulfonyl group and imino N atom, forming an alternating polymeric chain through the direction [0 1 0]. In 4, the inter-molecular N-H?O hydrogen bonds form one-dimensional polymeric chains through the a axis, and these linear chains are inter-connected to each other by N-H?O hydrogen bonds, which produce a chain of edge-fused R₄⁴ (16) and R₂² (12) rings along [1 0 0]. Complex 5 is a coordination polymer in which the monomeric [Ag(dmpen)(sac)]_n units are linked by Ag?Ag interactions, and the dmpen ligand acts as a bridge between the silver(I) ions, forming a two-dimensional network parallel to the (1 0 0) plane.

Full text of DOI:10.1016/j.ica.2010.02.013

Inorganica Chimica Acta 363 (2010) 1849–1858
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Syntheses, thermal analyses, crystal structures and antimicrobial properties
of silver(I)-saccharinate complexes with diverse diamine ligands
a,*
b
c
a
b
_
_
Okan Zafer Ye ßs ilel , Gökhan Ka ßs ta ßs , Cihan Darcan , Inci Ilker , Hümeyra Pa ßs ao g˘ lu ,
b
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
Department of Biology, Faculty of Arts and Sciences, Dumlupınar University, Kütahya, Turkey
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 July 2009
Received in revised form 7 January 2010
Accepted 13 February 2010
Available online 19 February 2010
Five new silver(I)-saccharinate complexes [Ag (sac) (tmen) ] (1), [Ag (sac) (deten) ] (2), [Ag (sac) (d-
2
2
2
2
2
2
2
2
0
0
men)
2
] (3), [Ag(sac)(N,N-eten)] (4), and [Ag(sac)(dmpen)]
n
(5); (sac = saccharinate, tmen = N,N,N ,N -tet-
0
0
ramethylethylenediamine, deten = N,N -diethylethylenediamine, dmen = N,N -dimethylethylenediamine,
N,N-eten = N,N-diethylethylenediamine and dmpen = 1,3-diamino-2,2-dimethylpropan) have been syn-
thesized and characterized by elemental analyses, IR, thermal analyses, single crystal X-ray diffraction
and antimicrobial activities. The crystallographic analyses show that all the complexes crystallize in
Keywords:
1
monoclinic space group P2 /c. In 1, the sac ligand acts as a bridge to connect the silver centres through
Saccharinate complexes
Silver(I) complexes
Antimicrobial properties
Coordination polymer
its imino N and carbonyl O atoms forming an eight-membered bimetallic ring in a chair conformation.
Complex 2 has also a dimeric structure in which the monomeric [Ag(sac)(deten)] units are linked by
Agꢀ ꢀ ꢀAg interactions. In 3, saccharinate ligand acts as a bridging bidentate ligand between two silver(I)
centres through sulfonyl group and imino N atom, forming an alternating polymeric chain through the
direction [0 1 0]. In 4, the inter-molecular N–Hꢀ ꢀ ꢀO hydrogen bonds form one-dimensional polymeric
chains through the a axis, and these linear chains are inter-connected to each other by N–Hꢀ ꢀ ꢀO hydrogen
4
2
bonds, which produce a chain of edge-fused R ð16Þ and R ð12Þ rings along [1 0 0]. Complex 5 is a coor-
4
2
dination polymer in which the monomeric [Ag(dmpen)(sac)]
and the dmpen ligand acts as a bridge between the silver(I) ions, forming a two-dimensional network
parallel to the (1 0 0) plane.
n
units are linked by Agꢀ ꢀ ꢀAg interactions,
Ó 2010 Elsevier B.V. All rights reserved.
1
. Introduction
The rational design and synthesis of one-, two- and three-
ligand and coordinated to metals by means of its nitrogen atom,
carbonyl oxygen or sulfonyl oxygen atoms. The most common
coordination mode of sac is ligation through the nitrogen atom,
whereas coordination through the carbonyl or sulfonyl oxygen is
less common [29]. To the best of our knowledge, until now the
structural characterization of sac, too much mononuclear M(II)-
saccharinate complexes with N- and O-donor ligands (M = Mn(II),
Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)), was reported [29–
34]. However X-ray crystal structures of both dinuclear, polynu-
clear and silver(I)-saccharinate complexes have appeared rarely
in the literature [35–45].
Due to the outbreak of infectious diseases caused by different
pathogenic bacteria and the development of antibiotic resistance,
researchers are searching for new antibacterial agents. Therefore,
new antimicrobial agents and nanotechnological materials have
to be synthesized for the treatment of resistant bacterial diseases
[46]. The antibacterial property of silver has been known for thou-
sands of years [47]. Silver nanoparticles have proved to be most
effective as they have good antimicrobial efficacy against bacteria,
viruses and other eukaryotic microorganisms [48]. Silver is toxic to
dimensional frameworks based on transition metals and polyfunc-
tional-bridging ligands are of great research interest, due to the no-
vel structural topologies examined and potential applications as
functional materials [1–17]. As known, silver(I) ion, as a soft acid,
coordinating to soft bases such as S- and N-containing ligands
are a favorable building block for coordination polymers [18–23],
since it principally exhibits linear, bent, trigonal planar, T-shaped,
tetrahedral, trigonal pyramidal coordination in its metal com-
plexes with different ligands [24–27]. Furthermore, Ag(I) ion is
apt to form short Agꢀ ꢀ ꢀAg 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 spe-
cial properties [7]. Saccharin is widely used as a no calorie sweet-
ener and food additive [28] and its anion acts as a polyfunctional
*
Corresponding author. Tel.: +90 2222393750; fax: +90 2222393578.
E-mail address: yesilel@ogu.edu.tr (O.Z. Ye sß ilel).
0
020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.02.013

1
850
O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
microorganisms by poisoning respiratory enzymes and compo-
nents of electron transport system, and it also binds to bacterial
surface, altering the membrane function [49] and inhibiting repli-
cation [50,51].
Silver compounds are used as antimicrobial agents in a variety
of applications, including coating of catheters, dental resin com-
posites, burn wounds and homeopathic medicine, antimicrobial
matter with a minimal risk of toxicity in humans [52]. [M(sa-
O
O
O
O
O
O
S
S
S
N
O
N
O
Ag
N
O
Ag
Ag
Ag
Ag
(
I)
(II)
(III)
c)
2
(H
2
O)
4
]ꢀ2H
2
O (where M = Mn, Fe, Co, Ni, Cu and Zn) possess
Scheme 1. Coordination modes of saccharinate ligand (I = 2, 4, 5; II = 1; III = 3).
2
ꢁ
the ability to dismutate the O anion. Metal complexes present
the most important activity. It has also been commented that thio-
saccharin and some of its derivatives have potent antimicrobial
activity [29,53,54]. Metal ligands and complexes have been evalu-
ated for their biological activities against selected pathogens and
cancer cell lines [55–58].
Using sac ligand, herein we report the synthesis, spectroscopic,
thermal and antimicrobial properties and characterization of five
new (saccharinato)silver(I) complexes with diverse diamine deriv-
atives, N,N,N’,N’-tetramethylethylenediamine, N,N’-diethylethyl-
enediamine,
diethylethylenediamine and 1,3-diamino-2,2-dimethylpropan li-
gands, namely [Ag (sac) (tmen) (1), [Ag (sac) (deten) (2),
Ag (sac) (dmen) (3), [Ag(sac)(N,N-eten)] (4) and [Ag(sac)(dm-
pen)] (5).
N,N’-dimethylethylenediamine,
N,N-
2
2
2
]
2
2
2
]
[
2
2
2 n
]
n
2
. Results and discussion
The relevant crystal data and experimental conditions along
with the final parameters are summarized in Table 1. The saccha-
rinate ligand acts as a monodentate or bridging ligand with three
different coordination modes (Scheme 1).
2 2 2
2.1. [Ag (sac) (tmen) ] (1)
In complex 1, each sac anion adopts a
nect with two silver ions through its imino N and carbonyl O
atoms, forming binuclear [Ag (sac) ] units (Fig. 1). Thus, a chair
conformation of eight-membered bimetallic ring (r.m.s. deviation
is 0.267 Å) is formed by two silver(I) ions linked by two NꢁCꢁO
bridges. A similar structure but with a planar bimetallic ring
2
l -bridging mode to con-
Fig. 1. Dimeric unit in 1 with the atom-labeling scheme and 50% thermal ellipsoids.
H atoms have been omitted for clarity [Symmetry code: (i) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z].
2
2
(
[
r.m.s. deviation is 0.099 Å) has been reported for silver(I) complex
Ag -sac) -hep) [43]. In the structure, the Ag(I) ions are
The coordination geometry around the silver ions is considered
i
2
(l
2
(l
2
]
n
to be a distorted tetragon [N1ꢁAg1ꢁO1 = 136.9(1)°, N1ꢁAg1ꢁN2 =
four-coordinated by two nitrogen atoms from tmen ligand, one N
atom from sac ligand and one O atom from another sac ligand.
122.4(1)°, N1ꢁAg1ꢁN3 = 107.6(1)°, N2ꢁAg1ꢁN3 = 76.5(1)°]. The
selected bond lengths and angles are given in Table 2. The AgꢁN
Table 1
Crystallographic data and structure refinement parameters for complexes 1–5.
Complexes
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
26
H
40Ag
2
N
6
O
S
6 2
C
26
H
40Ag
2
N
6
O
S
6 2
C
11
H
16AgN
3
O
3
S
C
13
H
20AgN
3
O
3
S
C
12 3 3
H18AgN O S
812.50
monoclinic
P2 /c
8.2691(5)
16.2505(10)
12.4581(7)
102.133(4)
1636.69(17)
2
812.50
monoclinic
P2 /c
9.0652(5)
13.7040(5)
13.9759(8)
110.936(4)
1621.59(14)
2
1.38
1.664
378.20
monoclinic
P2 /c
21.8001(9)
11.8830(3)
26.2919(12)
123.423(3)
5684.6(4)
16
406.25
monoclinic
P2 /c
8.0219(4)
16.4646(6)
14.0701(7)
119.123(4)
1623.40(13)
4
1.38
1.662
392.22
monoclinic
P2 /c
11.7603(7)
12.8760(7)
10.3877(6)
90.765(5)
1572.82(16)
4
1.42
1.656
1
1
1
1
1
b (Å)
c (Å)
b (ꢀ)
V (Å )
3
Z
l
D
(mm 1
ꢁ
)
1.37
1.649
1.57
1.768
calc (Mg mꢁ3)
Crystal size (mm)
h Range (°)
0.45 ꢂ 0.35 ꢂ 0.26
0.56 ꢂ 0.40 ꢂ 0.30
0.41 ꢂ 0.33 ꢂ 0.10
0.59 ꢂ 0.40 ꢂ 0.29
0.33 ꢂ 0.28 ꢂ 0.17
1.7–28.1
1.6–28.0
1.6–26.1
1.7–28.1
1.6–28.0
Measured reflections
24 367
22 583
56 773
25 236
18 740
Independent reflections
3714
3135
11224
3496
3037
R
1
, wR
2
0.029, 0.076
1.05
0.29, ꢁ0.77
0.045, 0.116
1.08
0.99, ꢁ1.39
0.062, 0.166
0.89
4.42, ꢁ0.85
0.045, 0.122
1.07
0.50, ꢁ1.81
0.040, 0.105
1.06
1.04, ꢁ1.23
2
Goodness-of-fit on F
D
ꢁ
3
q
max
,
D
q
min (e Å
)

O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
1851
Table 2
bond distances are in the range of 2.206(2)ꢁ2.460(2) Å, and the
AgꢁNsac distance is the shortest one. The bite angle of tmen ligand
is 76.5(1)°. The ring of sac is planar with a r.m.s. deviation of
0.0105 Å. The Agꢀ ꢀ ꢀAg separation within the metallocycle is
3.372 Å. The molecular packing of the complex is stabilized by C–
Selected bond distances (Å), angles (°) and C–Hꢀ ꢀ ꢀ
p interactions for 1.
Bond lengths (Å)
Angles (°)
i
Ag1ꢁN1
Ag1ꢁN2
Ag1ꢁN3
2.206(2)
2.455(2)
2.460(2)
2.327(2)
1.236(3)
1.342(3)
3.372
N1ꢁAg1ꢁO1
136.9(1)
122.4(1)
107.6(1)
124.2(2)
76.5(1)
N1ꢁAg1ꢁN2
N1ꢁAg1ꢁN3
Hꢀ ꢀ ꢀ
p
interactions. The details of these interactions are given in Ta-
(sac) (tmen) ] molecules are inter-con-
i
i
Ag1ꢁO1
C1ꢁO1ꢁAg1
N2ꢁAg1ꢁN3
O1ꢁC1ꢁC2
ble 2. The individual [Ag
2
2
2
C1ꢁO1
N1ꢁC1
iii
nected to each other by C10ꢁH10aꢀ ꢀ ꢀCgA interactions (CgA: C2–
C3–C4–C5–C6–C7, (iii) 1 ꢁ x, ½ + y, 1.5 ꢁ z). This is resulted in a
two-dimensional network parallel to the (1 0 0) plane as illustrated
121.7(2)
29.6(3)
i
i
Ag1ꢀ ꢀ ꢀAg1
XꢁH(I)
N1ꢁC1ꢁO1ꢁAg1
Cg (J)
Hꢀ ꢀ ꢀCg (Å)
X–Hꢀ ꢀ ꢀCg (°)
in Fig. 2(a). It is found that the [Ag
2
(sac)
also linked by C8ꢁH8aꢀ ꢀ ꢀCgA ((ii) 1 + x, y, z) interactions
Fig. 2(b)), forming a one-dimensional linear chain through the
direction [1 0 0].
2 2
(tmen) ] molecules are
C8ꢁH8a
CgAii
2.91
2.77
167
160
ii
iii
C10ꢁH10a
CgA
(
Symmetry codes: (i) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z; (ii) 1 + x, y, z; (iii) 1 ꢁ x, ½ + y, 1.5 ꢁ z.
iii
ii
Fig. 2. The molecular packing of 1 showing the inter-molecular C–Hꢀ ꢀ ꢀring interactions: (a) C10ꢁH10aꢀ ꢀ ꢀCgA and (b) C8ꢁH8aꢀ ꢀ ꢀCgA , hydrogen and methyl groups are
omitted for clarity. Symmetry codes are as given in Table 2.

1
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O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
2 2 2
2.2. [Ag (sac) (deten) ] (2)
2 2 2
2.3. [Ag (sac) (dmen) ] (3)
Complex 2 has also a dimeric structure which consists of mono-
Complex 3 has the same structure as that reported by Yilmaz
et al. [59]. However, both complexes have different unit-cell
parameters. These complexes consist of two crystallographically
meric [Ag(sac)(deten)] units linked by Agꢀ ꢀ ꢀAg interactions (Fig. 3).
Each silver(I) centre is three-coordinated by an N-bonded sac li-
gand and bidentate-chelating deten ligand, exhibiting a distorted
T-shaped coordination environment. The AgꢁN bond distances
range from 2.140(3) Å to 2.337(4) Å. Among the AgꢁN bonds, the
AgꢁNsac bond is the shortest one and due to the relatively small
bite angle [77.9(2)°] of deten, the silver-deten lengths are signifi-
cantly stretched. The selected bond lengths and angles together
with hydrogen-bonding geometry are collected in Table 3. The
Agꢀ ꢀ ꢀAg separation in dimeric unit is 3.040 Å. The crystal packing
is provided by intra-molecular N–Hꢀ ꢀ ꢀO hydrogen bonds between
the NH groups of deten ligands and sulfonyl O atoms of sac ligands
2 2 2
independent [Ag (sac) (dmen) ] building blocks in the unit-cell
(Fig. 4), however, in complex 3 these blocks are further bridged
by sulfonyl groups of the sac ligands although the sulfonyl group
is less basic and only occasionally involves in coordination. There
are only a few examples for this bridging behavior of sac ligand
[35,41,60,61]. Apart from those reported in the literature, dimeric
units in complex 3 show an alternating arrangement and inter-
estingly, each silver(I) ion is four- or five-coordinated in this
arrangement (Fig. 5). The Agꢀ ꢀ ꢀAg separations in the dimeric
units are 3.348 and 3.375 Å, being longer than those reported
by Yilmaz et al. [59]. The AgꢁNsac bond distances are in a narrow
range of 2.125(6)–2.145(6) Å and these values are comparable to
the corresponding values in complex 2 [2.140(3) Å] and those re-
(
Table 3).
ported for dimeric saccharinate complexes [Hg
2 4 2
(sac) (mpy) ]
[
2.094(2) and 2.106(2) Å] [62] and [Ag (sac) (dmen)
2
2
2
] [2.127(6)
and 2.123(6) Å] [59]. The selected bond distances and angles
are given in Table 4. In the extended structure, one-dimensional
polymeric chains are reinforced by NꢁHꢀ ꢀ ꢀO hydrogen bonds be-
2
tween the NH groups of dmen ligands and neighboring sac li-
gands. The details of hydrogen bond geometry are given in
Table 4.
2.4. [Ag(sac)(N,N-eten)] (4)
Complex 4 consists of monomeric [Ag(sac)(N,N-eten)] units.
Each silver(I) centre is three-coordinated by N-bonded sac ligand
and bidentate-chelating N,N-eten ligand, which exhibits a dis-
3
torted T-shaped AgN coordination environment (Fig. 6). In 4,
the Ag–N bond distances range from 2.120 to 2.506 Å. Among
the Ag–N bonds, silver-sac bond is the shortest, and due to rela-
tively small bite angle [77.5(1)°] of the ligand N,N-eten-silver
lengths are significantly stretched. The selected bond distances
and angles along with hydrogen bond geometry are collected in
Table 5.
The crystal structure of 4 is mainly stabilized by inter-molecular
NꢁHꢀ ꢀ ꢀO hydrogen bonds. The N,N-eten ligands are involved in
hydrogen bonds through their amine hydrogen atoms (H2a and
H2b) with the sulfonyl and carbonyl O atoms of neighboring sac li-
ii
gands. It is seen from Fig. 7 that inter-molecular N2ꢁH2aꢀ ꢀ ꢀO1
hydrogen bonds give rise to one-dimensional polymeric chains
running through the a axis. These linear chains are inter-connected
i
to each other by N2ꢁH2bꢀ ꢀ ꢀO3 hydrogen bonds, which produce a
4
2
chain of edge-fused R ð16Þ and R ð12Þ rings along [1 0 0]. As is seen
4
2
from Fig. 8, the inter-molecular
atoms of N,N-eten ligands and the sac rings (hereafter A) are also
p
ꢀ ꢀ ꢀring interactions between H
Fig. 3. Molecular structure of 2 with atom-labeling scheme. Some hydrogen atoms
are omitted for clarity [Symmetry code: (i) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z].
effective in the molecule packing, leading to a sheet structure par-
iii
allel to bc plane. The details of C10ꢁH10bꢀ ꢀ ꢀCgA (CgA: C2–C3–
iv
C4–C5–C6–C7, (iii) ꢁx, 1 ꢁ y, 1 ꢁ z) and C12ꢁH12bꢀ ꢀ ꢀCgA ((iv) x,
1
,5 ꢁ y, ꢁ1/2 + z) interactions are given in Table 5.
Table 3
Selected geometric parameters and hydrogen bond geometry for 2.
2
.5. [Ag(sac)(dmpen)]
n
(5)
Bond lengths (Å)
Angles (°)
Ag1ꢁN1
Ag1ꢁN2
Ag1ꢁN3
2.140(3)
2.306(4)
2.337(4)
3.040
N1ꢁAg1ꢁN2
N1ꢁAg1ꢁN3
N2ꢁAg1ꢁN3
137.6(2)
140.1(2)
77.9(2)
Molecular structure of 5 is shown in Fig. 9. The selected bond
distances and angles together with hydrogen-bonding geometry
are collected in Table 6. Complex 5 is a coordination polymer in
i
Ag1ꢀ ꢀ ꢀAg1
n
which the monomeric [Ag(sac)(dmpen)] units are linked by
D–Hꢀ ꢀ ꢀA
Hꢀ ꢀ ꢀA (Å)
2.36(5)
2.48(6)
Dꢀ ꢀ ꢀA (Å)
3.147(7)
3.248(6)
D–Hꢀ ꢀ ꢀA (°)
162(4)
176(6)
Agꢀ ꢀ ꢀAg interactions, and the dmpen ligand acts as a bridge be-
tween the silver(I) ions, forming a two-dimensional network as
shown in Fig. 10. The coordination geometry around the silver(I)
ion is considered T-shaped rather than trigonal, because of the
i
N2ꢁH2aꢀ ꢀ ꢀO1
i
N3ꢁH3aꢀ ꢀ ꢀO2
Symmetry code: (i) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z.

O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
1853
Fig. 4. The molecular structure of 3 showing the labeling of non-hydrogen atoms in two crystallographically independent molecules. Displacement ellipsoids are plotted at
the 50% probability level. Hydrogen atoms are omitted for clarity.
Fig. 5. A fragment of the one-dimensional [0 1 0] polymeric chain of 3. All H atoms, methyl groups and phenyl rings are omitted for clarity.
significant deviation from the ideal trigonal geometry [N1–Ag1–
N2 = 120.2(1)°, N3–Ag1–N1 = 96.0(1)°, N2–Ag1–N3 = 142.6(1)°].
The Ag–N bond distances are in the range of 2.214(3)–2.379(3) Å
and the Agꢀ ꢀ ꢀAg separation is 3.118 Å. The sac moiety is planar
with an r.m.s. deviation of 0.0296 Å. The saccharinate intraligand
bond distances have similar values to those observed for com-
2.6. Thermal properties
The thermal decomposition pathways of five Ag(I)-saccharinate
complexes were followed up to 1000 °C in air atmosphere.
2.7. [Ag
2
(sac)
2
2
(tmen) ] (1)
2
plexes 1 –4. The NH groups of dmpen ligands are involved in
hydrogen bonds with the carbonyl and sulfonyl O atoms of neigh-
boring sac ligands. The details of hydrogen bond geometry are gi-
ven in Table 6.
The [Ag
2
(sac)
2
(tmen) ] complex exhibits three decomposition
2
stages (Fig. S1) and stable up to 134 °C. In the first stage, endother-
mic removal of one tmen ligand occurs in the temperature range of

1
854
O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
Table 4
plexes, the TG curves exhibit a continuous mass loss. Therefore,
Selected geometric parameters for 3.
it is almost impossible to calculate the mass loss value for each
step. The stages at the temperature range of 163–388 °C for 2
and 141–387 °C for 3 are related to the successive decomposition
of ligands by giving exothermic effect. The following stage involves
the highly exothermic decomposition of the remaining organic
part. The mass loss calculations suggest that the residue left as a
final product is metallic silver (found 74.17, calcd. 73.62% for 2
and found 71.21, calcd. 71.65% for 3).
Bond lengths (Å)
Angles (°)
Ag1ꢁN1
Ag1ꢁN2
Ag1ꢁN3
Ag2ꢁN4
Ag2ꢁN5
Ag2ꢁN6
Ag1ꢀ ꢀ ꢀAg2
2.125(6)
2.215(6)
2.571(6)
2.145(6)
2.197(6)
2.499(6)
3.348
N1ꢁAg1ꢁN2
N1ꢁAg1ꢁN3
N2ꢁAg1ꢁN3
N4ꢁAg2ꢁN5
N4ꢁAg2ꢁN6
N5ꢁAg2ꢁN6
Ag3ꢀꢀꢀAg4
166.2(2)
114.8(2)
76.7(2)
164.9(2)
115.8(2)
78.1(2)
3.375
D–Hꢀ ꢀ ꢀA
Hꢀ ꢀ ꢀA (Å)
Dꢀ ꢀ ꢀA (Å)
D–Hꢀ ꢀ ꢀA (°)
2
.9. [Ag(sac)(N,N-eten)] (4) and [Ag(sac)(dmpen)]
n
(5)
i
N11ꢁH11eꢀ ꢀ ꢀO9
2.50
2.20
2.19
2.45
2.12
2.08
3.387
3.101
3.066
3.183
2.959
2.913
171
178
165
138
154
153
i
N8ꢁH8cꢀ ꢀ ꢀO9
ii
Complexes start to decompose with melting at 147 and 171 °C,
N5ꢁH5bꢀ ꢀ ꢀO6
N11ꢁH11dꢀ ꢀ ꢀO8
N8ꢁH8dꢀ ꢀ ꢀO10
N5ꢁH5aꢀ ꢀ ꢀO1
respectively (Figs. S4 and S5). The following stages were observed
successively decomposition process in the TG curve of both com-
plexes. Therefore, it is impossible to calculate the mass loss value
for each step. The last exothermic stage between 438 and 634 °C
for 4; 453 and 576 °C for 5 (DTAmax = 594 °C) is related to the
decomposition of extremely burning organic residue. The final
decomposition products are metallic Ag.
Symmetry codes: (i) ꢁx, 1/2 + y, 1/2 ꢁ z; (ii) 1 ꢁ x, ꢁ1/2 + y, 3/2 ꢁ z.
2.10. Antimicrobial activities
In the present study, in vitro potential antimicrobial activity of
complexes 1–5 and Ag(I)–saccharin complex (6) was tested
according to both minimal inhibitory concentration and disc diffu-
sion method. The results are given in Tables 7 and 8. The com-
pounds were dissolved in DMSO. Antimicrobial activity was
measured for 40 lg/ml concentrations which was determined by
MIC against Gram positive (Staphylococcus aureus ATCC 6535, Bacil-
lus cereus ATCC 7064, Micrococcus luteus NRRLB 1018) and Gram
negative (Escherichia coli W3110, Proteus vulgaris NRRLB 2643,
Pseudomonas aeruginosa ATCC 27853) bacteria with the yeast (Can-
dida albicans ATCC 10231) and clinical isolate (Methicillin-resistant
Staphylococcus aureus, P. vulgaris and P. aeruginosa). Chloramphen-
icol, oflaxacin, rifampisin, cefuroxime, tetracycline, and nystatin
antibiotics were also used for comparison. The inhibition zones
are formed by standard antibiotic discs as shown in Table S1.
Antimicrobial activities of Ag saccharin and derivatives esti-
mated by MIC values are shown in Table 7. All the complexes
and ligands showed a good antimicrobial activity against the stud-
ied wild-type and clinical isolates. There are no significant differ-
ences among antimicrobial activities of new complexes.
Fig. 6. The molecular structure of 4 with atom-labeling scheme and thermal
ellipsoids at the 50% probability level. Hydrogen atoms are omitted for clarity.
Table 5
Selected geometrical data for 4.
Bond lengths (Å)
Angles (°)
Ag1ꢁN1
Ag1ꢁN2
Ag1ꢁN3
2.120(3)
2.189(4)
2.506(4)
N1ꢁAg1ꢁN2
N1ꢁAg1ꢁN3
N2ꢁAg1ꢁN3
160.8(2)
121.5(1)
77.5(1)
As can be seen clearly from Table 7, complex 6 is more efficient
against all bacteria and yeast than the new complexes except P.
aeruginosa. While the values of MIC for 6 are in the range of
D–Hꢀ ꢀ ꢀA
Hꢀ ꢀ ꢀA (Å)
2.12(6)
2.13(6)
Dꢀ ꢀ ꢀA (Å)
2.962(6)
2.994(5)
D–Hꢀ ꢀ ꢀA (ꢀ )
162(5)
149(5)
1
3.5–27.5
the values of MIC for new complexes (1–5) are in the range of
0–55 g/ml. Conspicuously, while the values of MIC for MRSA
clinic isolate is 9 g/ml, MIC of wild-type S. aureus is 13.5 g/ml.
lg/ml, value of MIC for P. aeruginosa is 45 lg/ml. But
i
N2ꢁH2bꢀ ꢀ ꢀO3
ii
N2ꢁH2aꢀ ꢀ ꢀO1
3
l
XꢁH(I)
C10ꢁH10b
C12ꢁH12b
Cg (J)
Hꢀ ꢀ ꢀCg (Å)
2.756
2.974
X–Hꢀ ꢀ ꢀCg (°)
165.6
143.2
l
l
iii
CgA
This result shows that 6 could be used against Staphylococcal
infections. MIC of new complexes is greater than 6. But dose used
for antimicrobial activity of new complexes is approximately same
as standard antibiotic dose. Therefore both 6 and new complexes
could be used as antimicrobial matter. Despite of structure of
new silver saccharinate complexes are different each other from,
there are not important differences in MIC values at all studied
microorganisms, so there was no correlation between the structure
of new complexes and antimicrobial activity.
iv
CgA
Symmetry codes: (i) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z; (ii) 1 + x, y, z; (iii) 2 ꢁ x, 1 ꢁ y, 1 ꢁ z; (iv) x, 1/
2
ꢁ y, 1/2 + z.
1
34–177 °C (DTAmax = 174 °C). The following two stages are in the
temperature range of 177–829 °C, and the complex involves the
decomposition of tmen and sac ligands by exothermic effects
(
DTAmax = 307, 522 °C). The decomposition product is metallic sil-
ver and total mass loss of 74.88% (calcd. 73.60%) agrees with the
proposed structure well.
As can be seen from Table 8, disc diffusion results show that 6 is
more effective than the new complexes. Cavicchioli et al. [64] re-
ported that Ag(I)-saccharinate, Ag(I)-aspartamate and Ag(I)-cycla-
2.8. [Ag (sac) (deten) ] (2) and [Ag (sac) (dmen) ]
2 2 2 2 2 2 n
(3)
mate have MIC values ranging from 9.75 to 124 lM against
environmental mycobacteria and tuberculosis agent, and they
were proposed to be a new candidate for the treatment of tubercu-
losis. In addition, metal complexes of saccharinato have been
Complex decompositions begin at 163 and 141 °C after melting
at 149 and 140 °C, respectively (Fig. S2 and Fig. S3). In both com-

O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
1855
4
4
2
2
Fig. 7. A stereo view of part of the crystal structure of 4 showing the formation of a chain of edge-fused R ð16Þ and R ð12Þ rings along [1 0 0]. Phenyl ring, some carbon and
hydrogen atoms are omitted for clarity [Symmetry codes: (i) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z; (ii) 1 + x, y, z].
Fig. 8. The C–Hꢀ ꢀ ꢀring interactions parallel to bc plane of 4. Hydrogen atoms and methyl groups are omitted for clarity.
demonstrated to possess antibacterial and antifungal properties,
and inhibitory action against some enzymes [54–56].
complexes and AgSD on S. aureus, but our new complexes have bet-
ter MIC values than silver fusidate on other studied microorgan-
ism. Also, N-heterocyclic carbenes are currently being explored
for treating cystic fibrosis lung infection [70].
Antimicrobial activities of complexes 1–5 and 6 did not show
differences between gram (+), gram (ꢁ) and eukaryotes in point
of effective dose. It is known that there are a disparity between
prokaryotes (gram +, gram ꢁ) and eukaryotes. But this difference
is not important for antimicrobial effect of silver-saccharinate
complexes.
Silver sulfadiazine (AgSD), a sulfa drug, is used to prevent and
treat infections of second- and third-degree burns. Silver is an
effective antimicrobial agent with low toxicity which is important
especially in the treatment of burn wounds [65,66]. AgSD cell com-
ponents include DNA and cause membrane damage [67]. Silver sul-
fadiazine is effective against bacteria such as E. coli, S. aureus,
Pseudomonas sp. and some antifungal and antiviral activities [68].
MIC values of new silver complexes are the same as those of AgSD.
MIC values of the newly synthesised Ag-saccharinate complexes
are better than those of AgSD on S. aureus [69]. Silver fusidate have
antimicrobial activity better than both new silver saccharinato
While there is no significant difference between wild-type and
clinical isolate at antimicrobial activities of Ag(I)-saccharinate
complexes, clinical isolates are resistant to standard antibiotics

1
856
O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
plexes could produce N- or O- coordination of the saccharinate an-
ion, as observed in [Cu
(sac) (Himid) ], [V(sac) (py) and
Ni(sac) (py) ] and recently in [Cu(sac) (Hpz) ] [63]. The reaction
of different diamine derivatives in water solution yielded com-
pounds with the formulas [Ag (sac) (tmen) ] (1), [Ag (sac) (de-
ten) ] (2), [Ag (sac) (dmen) ] (3), [Ag (sac)(N,N-eten)] (4) and
Ag(sac)(dmpen)] (5). The composition of the complexes was
2
4
4
2
4
]
[
2
4
2
4
2
2
2
2
2
2
2
2
2
2
[
n
determined by elemental, IR and thermal analysis in detail. Lastly,
their structures were determined by single crystal X-ray diffraction
technique.
3.2. General
All reagents were purchased from commercial sources and used
as supplied. IR spectra were obtained with a Perkin–Elmer 100 FT-
ꢁ1
IR spectrometer using KBr pellets in the 4000–400 cm range. Ele-
mental analysis for C, H and N was performed using a Carlo Erba
1
106 microanalyser. Diamond TG/DTA thermal analyzer was used
to record simultaneously TG, DTG and DTA curves in the static air
ꢁ1
atmosphere at a heating rate of 10 K min in the temperature
Fig. 9. The building block unit of 5 with the atom-labeling scheme and thermal
ellipsoids at the 50% probability level.
range of 50–1000 °C using platinum crucibles.
3.3. Synthesis of complexes
Table 6
A
solution of the N,N,N’,N’-tetramethylethylenediamine
Selected geometric parameters and hydrogen-bonding geometry for 5.
(
2 mmol, 2.32 g), N,N’-diethylethylenediamine (2 mmol, 2.32 g),
Bond lengths (Å)
Angles (°)
N,N’-dimethylethylenediamine (2 mmol, 1.76 g), N,N-diethylethyl-
enediamine (2 mmol, 2.32 g) and 1,3-diamino-2,2-dimethylpropan
ligands (2 mmol, 2.06 g) in water (10 mL) was added dropwise to
an aqueous solution of [Ag(sac)] (2 mmol, 0.58 g) and stirred
for 2 h at 30 °C. The reaction mixture was then slowly cooled to
Ag1ꢁN1
Ag1ꢁN2
Ag1ꢁN3
2.379(3)
2.214(3)
2.253(3)
3.118
N1ꢁAg1ꢁN2
N1ꢁAg1ꢁN3
N2ꢁAg1ꢁN3
120.2(1)
96.0(1)
142.8(1)
35
i
Ag1ꢀ ꢀ ꢀAg1
D–Hꢀ ꢀ ꢀA
Hꢀ ꢀ ꢀA (Å)
Dꢀ ꢀ ꢀA (Å)
D–Hꢀ ꢀ ꢀA (°)
room temperature. The crystals formed were filtered and washed
i
N2ꢁH2aꢀ ꢀ ꢀO1
2.31(6)
2.15(6)
2.26(6)
2.23(6)
3.095(5)
2.994(5)
3.021(5)
2.976(5)
158(5)
147(5)
164(6)
142(5)
with 5 mL of ethanol and dried in air. [Ag
for C26 : C, 38.44; H, 4.96; N, 10.34; S, 7.89. Found: C,
8.39; H, 5.04; N, 10.33; S, 7.89%. IR (KBr pellet, m/cm ) for 1: 3435
s, 3085 w, 2986 w, 2960 w, 2827 m, 2775 m, 1651 vs, 1626 vs, 1583
s, 1458 m, 1335 m, 1295 s, 1270 s, 1155 vs, 1054 w, 951 m, 759 m,
2 2 2
(sac) (tmen) ], Anal. Calc.
ii
N2ꢁH2bꢀ ꢀ ꢀO1
2 6 6 2
H40Ag N O S
i
N3ꢁH3aꢀ ꢀ ꢀO2
ꢁ1
3
N3ꢁH3bꢀ ꢀ ꢀO1
Symmetry codes: (i) 1 ꢁ x, 1 ꢁ y, 2 ꢁ z; (ii) 1 ꢁ x, 1/2 + y, 3/2 ꢁ z.
6
C
3
3
1
2 2 2
76 m, 605 m, 546 m, 460 w. [Ag (sac) (deten) ] (2), Anal. Calc. for
26
H
40Ag
2
N
6
O
6
S
2
: C, 38.44; H, 4.96; N, 10.34; S, 7.89. Found: C,
(
Table S1). It is determined that clinical isolates were more sensi-
ꢁ1
8.43; H, 5.01; N, 10.27; S, 8.02%. IR (KBr pellet,
m/cm ) for 2:
tive against 6 and five new complexes. Especially, while no MRSA
had effect on oflaxacin, rifampicin, cefuroxime that were used as
standard antibiotics, 6 and five new complexes had significantly
better antibacterial qualities. In a similar fashion, P. aeruginosa clin-
ical strain is resistant to chloramphenicol, rifampicin and cefurox-
ime, but Ag saccharin and new complexes are quite effective than
antibiotics.
421 m, 3297 m, 3261 m, 3082 w, 2969 m, 2919 w, 2851 m,
653 vs, 1625 vs, 1583 s, 1473 m, 1456 m, 1334 m, 1288 s, 1271
s, 1251 vs, 1154 vs, 948 s, 865 w, 762 m, 683 m, 606 m, 545 m,
2 6 6 2
53 w. [Ag (sac) (dmen) (3), Anal. Calc. for C22H32Ag N O S :
4
2
2
]
2 n
C, 34.93; H, 4.26; N, 11.11; S, 8.48. Found: C, 35.03; H, 4.21; N,
ꢁ1
1
1.09; S, 8.48%. IR (KBr pellet,
m
/cm ) for 3: 3435 m, 3331 m,
3
061 w, 2959 w, 2867 w, 2769 w, 1640 vs, 1625 vs, 1583 s, 1457
It is a well-known fact that hospital infections are quite impor-
tant for the public health and quite resistant against standard anti-
biotics. Therefore, there is an urgent demand for new antibiotics
and new class chemical formula that will efficiently inhibit the
growth of pathogenic microorganism. In this study, as part of our
efforts in the development of new metal-based antimicrobial com-
plexes, 6 and new complexes could be a new candidate for the
therapy of infectious diseases. This suggests that they are potent
as broad spectrum topical antimicrobial agents, but they need to
be investigated with respect to their toxicity.
m, 1331 m, 1258 s, 1152 vs, 1053 m, 956 s, 757 w, 679 m, 606
m, 543 m, 418 w. [Ag(sac)(N,N-eten)] (4), Anal. Calc. for C13 20Ag-
S: C, 38.44; H, 4.96; N, 10.34; S, 7.89. Found: C, 38.54; H, 4.61;
H
3 3
N O
ꢁ1
N, 10.30; S, 7.91%. IR (KBr pellet, m/cm ) for 4: 3338 m, 3278 m,
3
1
6
C
3
3
1
073 w, 2965 w, 2875 w, 2820 w, 1633 vs, 1583 vs, 1459 m,
342 m, 1264 vs, 1156 vs, 1051 m, 961 s, 878 w, 748 m, 678 w,
n
11 m, 536 m, 461 w. [Ag(sac)(dmpen)] (5), Anal. Calc. for
12
H
18AgN
3
O
3
S: C, 36.75; H, 4.63; N, 10.71; S, 8.17. Found: C,
ꢁ1
6.75; H, 4.60; N, 10.71; S, 8.11%. IR (KBr pellet,
m
/cm ) for 5:
435 m, 3336 m, 3326 m, 3275 m, 3062 w, 2951 m, 2868 w,
641 vs, 1625 vs, 1583 vs, 1458 m, 1333 m, 1258 vs, 1152 vs,
3
. Experimental
1053 m, 998 m, 966 m, 761 w, 743 m, 676 m, 606 m, 543 m, 454 w.
3.1. Synthesis
3.4. Antimicrobial activity studies
The aim of this work was to study the effects of diverse diamine
The antimicrobial activities were tested against standard Gram
positive (S. aureus ATCC6535, B. cereus ATCC7064 and M. luteus
NRRLB1018) and Gram negative ( E. coli W3110, P. vulgaris
NRRLB123, P. aeruginosa ATCC27853) bacterial strains, one yeast (
derivatives as co-ligands on the coordination mode of saccharinate
in mixed ligand complexes. Previous observations showed that a
second ligand in the coordination sphere of saccharinate com-

O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
1857
Fig. 10. A view of the two-dimensional framework in 5, parallel to (1 0 0). All hydrogen atoms and sac moieties are omitted for clarity.
Table 7
Minimal inhibitory concentration (MIC) values of the complexes against wild-type and clinical isolate microorganisms (
l
g/ml).
Complexes
Gram (+)
Gram (ꢁ)
Eukaryote
Clinical isolates
S. aureus
B. cereus
M. luteus
E. coli
P. vulgaris
P. aeruginosa
C. albicans
S. aureus (MRSA)
P. aeruginosa
P. vulgaris
1
2
3
4
5
6
32.5
42.5
32.5
37.5
37.5
13.5
32.5
35
32.5
37.5
35
37.5
35
32.5
30
35
22.5
37.5
52.5
45
35
35
37.5
40
32.5
32.5
32.5
19
42.5
40
40
40
55
37.5
37.5
37.5
32.5
37.5
27.5
32.5
42.5
32.5
37.5
40
45
40
42.5
47.5
40
32.5
40
40
40
32.5
21
22
27
45
9
40
Table 8
Antimicrobial assays of the compounds (40 lg/disc) against wild-type and clinical isolate microorganisms by disc diffusion method (diameter in mm).
Complexes
Gram (+)
Gram (ꢁ)
Eukaryote
Clinical isolate
S. aureus
B. cereus
M. luteus
E. coli
P. vulgaris
P. aeruginosa
C. albicans
S. aureus (MRSA)
P. aeruginosa
P. vulgaris
1
2
3
4
5
6
10
10
11
11
11
13
9
8
8
9
9
10
9
10
9
10
12
10
10
10
11
11
12
10
9
9
9
9
10
10
10
10
9
11
11
11
10
11
13
10
9
10
10
10
15
12
11
11
11
12
12
10
10
9
10
8
12
12
10
12
C. albicans ATCC10231) and clinical isolates (Methicillin resistant S.
aureus, P. vulgaris, P. aeruginosa) (Faculty of Medicine, Ondokuz
Mayıs University) by using disc diffusion and minimal inhibitory
concentration method.
McFarland turbidity standards. The nutrient broth (1 mL), contain-
ing the microorganisms, was transferred into test tubes and
800
added. The tubes were subjected to 2-fold serial dilution in nutri-
ent broth from 800 to 6.25 g/ml; eventually the ranges were nar-
lg/mL stock solutions of complexes of each compound was
For the broth dilution method, the cultures were grown in 5 ml
nutrient broth (Merck) at 37 °C for 18 h in shaking at 175 rpm. Bac-
terial and yeast cells were suspended in 50 ml Nutrient broth at a
l
rowed to define more exact values. All the test cultures were
grown at 37 °C in the shaker incubator. The incubation period
was 24 h for bacterial strains and 48 h for fungal strains. The
6
concentration of approximately 10 cells/mL by matching with 0.5

1
858
O.Z. Ye ßs ilel et al. / Inorganica Chimica Acta 363 (2010) 1849–1858
minimum inhibitor concentration, at which no growth was ob-
served, was taken as the MIC value ( g/ml) and this represents
the mean of at least three determinations. All the ligands and the
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Agar diffusion experiments were based on the obtained MIC
values by dilution methods. All stock solutions of the ligand and
the complexes were prepared in dimethylsulfoxide (DMSO, Merck)
according to the needed concentrations for experiments. Nutrient
Agar (Merck) plates were prepared and dried for 5 days at room
temperature. All the strains were grown in 5 ml nutrient broth at
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7 °C for 24 h. Bacterial and yeast cells were suspended in 5 ml
5
nutrient broth at a concentration of approximately 10 cfu/mL by
matching with 0.5 McFarland turbidity standards. The test strains
were spread on solid nutrient agar surface by using a sterile glass
rod. The final inoculation (inoculums) was approximately
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5
ꢁ1
1
0 cfu ml . At the same time, absorbent paper discs of 6 mm
for compounds were placed on agar surface and impregnated with
known concentrations (40 g for each disc) which were deter-
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mined previously by MIC tests. Antibiotic discs were placed on
the same agar plate. Chloramphenicol, oflaxacin, rifampicin, cefur-
oxime, and tetracycline were used as antibacterial control while
nystatin was used as the antifungal control for test microorgan-
isms. To ensure that the solvent had no effect on bacterial growth,
a control test was performed with the test medium supplemented
with DMSO as the same procedures as used in the experiments.
Incubation was done at 37 °C after inoculums and paper discs were
placed. Antimicrobial activity was indicated by the presence of
clear inhibition zones around the discs to be measured in diame-
ters and expressed in millimeters. All the tests were repeated three
times and average data were taken as the final results.
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Appendix A. Supplementary material
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CCDC 690781, 690782, 690783, 690784 and 690785 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. Supplemen-
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version, at doi:10.1016/j.ica.2010.02.013.
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