Synthesis and characterization of new Ag(I) coordination networks based on saccharinate and bis(isopropylimidazole) ligands exhibiting very close C–H?Ag interactions

Article abstract of DOI:10.1016/j.poly.2016.11.029

Two Ag(I) coordination networks, formulated as [Ag(sac)(μ-bisopib)]_n(1) and [Ag(sac)(μ-pbisopix)]·H₂O (2), have been synthesized based on the bis(isopropylimidazole) ligands 1,4-bis(2-isopropyl-1H-imidazol-1-yl)butane (bisopib) and 1,4-bis((2-isopropyl-1H-imidazol-1-yl)methyl)benzene (pbisopix), respectively, along with saccharinate (sac) ligands. All the complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction studies. The X-ray crystallographic studies of 1 and 2 revealed that the Ag(I) ions are μ-bridged by the bis(isopropylimidazole) derivative ligands to generate 1D zig-zag polymer and dinuclear structures, respectively. As far as we know, complex 1 shows the closest C–H?Ag interaction distance among similar literature examples. In complex 1 adjacent 1D coordination polymers are further joined by C–H?O hydrogen bonds and π?π interactions, generating a 3D supramolecular network. The C–H?O hydrogen bonds and C–H?π interactions play a crucial role in the architecture of the 3D network of complex 2. Thermal decompositions and photoluminescent properties of the Ag(I) complexes are also discussed herein.

Full text of DOI:10.1016/j.poly.2016.11.029

Accepted Manuscript
Synthesis and characterization of new Ag(I) coordination networks based on
saccharinate and bis(isopropylimidazole) ligands exhibiting very close C–H· ·
·
Ag interactions
Fatih Semerci, Hakan Erer, Onur Şahin
PII:
S0277-5387(16)30612-X
DOI:
http://dx.doi.org/10.1016/j.poly.2016.11.029
POLY 12337
Reference:
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Revised Date:
Accepted Date:
26 August 2016
8 November 2016
13 November 2016
Please cite this article as: F. Semerci, H. Erer, O. Şahin, Synthesis and characterization of new Ag(I) coordination
networks based on saccharinate and bis(isopropylimidazole) ligands exhibiting very close C–H· · ·Ag interactions,
Polyhedron (2016), doi: http://dx.doi.org/10.1016/j.poly.2016.11.029
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Synthesis and characterization of new Ag(I) coordination networks
based on saccharinate and bis(isopropylimidazole) ligands exhibiting very close C–
H···Ag interactions
a,*
b
c
Fatih Semerci , Hakan Erer , Onur Şahin
a
Department of Energy Systems Engineering, Faculty of Technology, Kırklareli University,
3
9000 Kırklareli, Turkey
b
Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University,
2
6480 Eskişehir, Turkey
c
Scientific and Technological Research Application and Research Center, Sinop University,
Sinop, Turkey
*Corresponding Author:
E-mail: fsemerci@klu.edu.tr; f_semerci@hotmail.com
Fax: +902882142084, Tel: +902882142082
1

Abstract
Two Ag(I) coordination networks, formulated as [Ag(sac)(µ-bisopib)] (1) and [Ag(sac)(µ-
n
bisopix)]·H O (2), have been synthesized based on the bis(isopropylimidazole) ligands 1,4-
2
bis(2-isopropyl-1H-imidazol-1-yl)butane (bisopib) and 1,4-bis((2-isopropyl-1H-imidazol-1-
yl)methyl)benzene (bisopix), respectively, along with saccharinate (sac) ligands. All the
complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray
diffraction studies. The X-ray crystallographic studies of 1 and 2 revealed that the Ag(I) ions
are µ-bridged by the bis(isopropylimidazole) derivative ligands to generate 1D zig-zag
polymer and dinuclear structures, respectively. As far as we know, complex 1 shows the
closest C-H···Ag interaction distance among similar literature examples. In complex 1
adjacent 1D coordination polymers are further joined by C-H···O hydrogen bonds and π···π
interactions, generating a 3D supramolecular network. The C-H···O hydrogen bonds and C-
H···π interactions play a crucial role in the architecture of the 3D network of complex 2.
Thermal decompositions and photoluminescent properties of the Ag(I) complexes are also
discussed herein.
Keywords: Coordination polymers; Saccharinate complexes; Ag(I) complexes, C-H···Ag
interaction
2

1
.
Introduction
The synthesis of metal organic networks based on transition metals and bis(imidazole) ligands
is an important research area, owing to a new type of supramolecular interactions and the
potential applications of these products [1-8]. The synthesis of metal organic networks relies
on certain factors, such as the nature of the metal ions and the coordination ability of the
ligands [9,10]. Hydrogen bonding plays an important role in structural chemistry, catalysis
and biologic processes [11-13].
Bis(imidazole) ligands containing aliphatic or aromatic groups are a good option for choosing
an N-donor ligand and when they are coordinated by transition metal ions, structural diversity
can be observed due to the rotation ability of such flexible ligands [5]. Coordination polymers
of flexible bis(imidazole) ligands such as 1,2-, 1,3- and 1,4-bis(imidazol-1-ylmethyl)benzene
have been appearing commonly in the literature [14-17]. Saccharin is an artificial sweetener
and is chosen because it is a polyfunctional ligand and shows coordination to metal atoms
through its imino nitrogen, carbonyl and sulfonyl oxygen atoms, as such its anions may act as
bridging ligands in various coordination modes [18-25].
The most controversial hydrogen bond type is the C–H···M weak interaction [26]. During the
last decade, new types of hydrogen bonding specific for Ag(I) complexes were found and
investigated [27-31]. Ag(I) ions possess d-type paired electrons, so it was assumed that they
could behave as acceptors to aliphatic and/or aromatic hydrogen atoms. Research on the usage
of C–H···Ag interactions is rare in the coordination chemistry of Ag(I) complexes, whereas
C–H···Ag interactions in building new metal organic networks have attracted attention. In
this study, to investigate C–H···Ag interactions we used bis(isopropylimidazole) ligands.
Ag(I)-Sac complexes have been synthesized due to their interesting structural properties
[
23,25,32-45]. To further investigate the influence of the bis(isopropylimidazole) derivative
3

ligands on the formation of supramolecular architectures of Ag(I)-saccharinate complexes,
two bis(isopropylimidazole) containing ligands, flexible 1,4-bis(2-isopropyl-1H-imidazol-1-
yl)butane (bisopib) and semi-flexible 1,4-bis((2 isopropyl-1H-imidazol-1 yl)methyl)benzene
(
pbisopix) (Scheme 1) were chosen as neutral ligands in this work. Bisopib and pbisopix are
bidentate ligands with flexible aromatic or aliphatic skeletons which contain methylene
groups. When coordinating to metal centers, the different flexibilities and steric effects of
these ligands may diversify the topologies of the networks.
In this paper, we describe the syntheses of two new Ag(I)-saccharinate complexes,
[
Ag(sac)(µ-bisopib)]
n
2
(1) and [Ag(sac)(µ-bisopix)]·H O (2). In the complexes, the
bis(isopropylimidazole) ligands show the ability to build the complexes and they play an
important role in directing the final networks. The crystal structures of these complexes and
an investigation of the effect of the sac anions and bis(isopropylimidazole) ligands on the
ultimate network is discussed.
2
2
. Experimental
.1. Measurements and materials
All starting materials were of analytical reagent grade and used as received without further
purification. The bisopix and bisobip ligands were synthesized according to the literature [4].
Elemental analyses for C, H, and N were carried out at the TÜBİTAK Marmara Research
-1
Centre. The IR spectra were recorded in the range 4000-400 cm by means of a Bruker
Tensor 27 FT-IR spectrometer with KBr pellets. The photoluminescence (excitation and
emission) spectra for the solid sample of the complexes were determined with a Perkin-Elmer
LS-55 spectrophotometer using a slit width of 15 nm excitation and 7 nm emissions at room
temperature. A Perkin Elmer Diamond TG/DTA thermal analyzer was used to record
4

simultaneous TG, DTG and DTA curves in a static air atmosphere at a heating rate of 10 ºC
-1
min in the temperature range 30-700 ºC using platinum crucibles.
2
.2. Crystallographic analyses
Suitable crystals of 1 and 2 were selected for data collection, which was performed on a D8-
QUEST diffractometer equipped with graphite-monochromatic Mo-K radiation at 296 K.
α
The structures were solved by direct methods using SHELXS-97 [1] and refined by full-
2
matrix least-squares methods on F using SHELXL-2013 [2]. All non-hydrogen atoms were
refined with anisotropic parameters. The H atoms of the C5 atom in 1 and O4 and C26 atoms
in 2 were located in a difference map refined subject to a DFIX restraint. The other H atoms
of C atoms were located from different maps and then treated as riding atoms with C-H
distances of 0.93-0.98 Å. Some atoms of the sac ligand in 1 and the pbisopix ligand in 2 are
disordered, which results in symmetrical disorder. The refinements of the disorders were
made anisotropically using PART and EADP restrictions. These disorders were modelled as
two different orientations with occupancy factors of 0.50 and 0.50. The following procedures
were implemented in our analysis, data collection: Bruker APEX2 [3]; program used for
molecular graphics: MERCURY programs [4]; software used to prepare material for
publication: WinGX [5]. Details of the data collection and crystal structure determinations are
given in Table 1.
2
.3. Preparation of the complexes
A mixture of Na(sac)·H O (0.50 g, 2.24 mmol) and AgNO (0.38 g, 2.24 mmol) was stirred in
2
3
water (20 mL) at 60 °C for 30 min and then bisopib (0.61 g, 2.24 mmol) was added to the
mixture. A solution of ammonia was added until the suspension dissolved. The solution was
stirred for 60 min and then filtered. The resulting solution was kept in the dark at room
5

temperature for 2 days to produce colorless crystals of 1. Yield: 0.859 g, 68% (based on
AgNO ). Anal. Calc. for C23 S: C, 48.94; H, 5.36; N, 12.41% Found: 49.24; H,
.88; N, 13.22%. IR (KBr, cm ): 3138(m), 3115(s), 2954(s), 2922(m), 2862(w), 1663(vs),
3
H30AgN
5
O
3
-
1
4
1
6
591(w), 1491(m), 1456(m), 1327(w), 1285(vs), 1153(s), 1070(m), 958(s), 760(m), 729(w),
79(w), 600(w), 542(w), 449(w)
The synthetic procedure for 2 was similar to that of 1, except that pbisopix was replaced by
bisopib (0.722 g, 2.24 mmol). After three days, colorless crystals of 2 were obtained. Yield:
0
1
2
1
3 5 4
.83 g, 59% (based on AgNO ). Anal. Calc. for C27H32AgN O S: C, 51.43; H, 5.12; N,
-1
1.11% Found: C, 51.27; H, 4.98; N, 11.42%. IR (KBr, cm ): 3410(br), 3120(m), 2968(s),
930(m), 2866(w), 1651(vs), 1587(w), 1516(m), 1490(s), 1456(m), 1365(w), 1340(w),
269(vs), 1149(vs), 1070(m), 959(s), 750(m), 731(w), 679(w), 602(w), 538(w), 426(w)
3
3
. Results and discussion
.1. Synthesis and spectral characterization
The reaction of bisopib and pbisopix with saccharinate ligands and Ag(I) ions in
diluted ammonia solution at room temperature resulted in the crystallization of the silver
complexes 1 and 2. Elemental analysis for complexes 1 and 2 agreed with the formula of the
complexes, as confirmed by X-ray single crystal analysis. Moreover, microanalysis data
confirmed the 1:1 ratio of silver ions to sac and bisopib or pbisopix ligands in the complexes.
Both complexes were obtained as colorless crystals in high yields of over 60%.
The complexes were investigated by FT-IR spectroscopy (Fig. S1.). Selected absorption
bands of the complexes are presented in Table 2, together with the FT-IR data of [Ag(sac)]
[
46] and [Ag
2
(sac)
2
(o-bix) ] (o-bix = 1,2-bis(imidazole-1-ylmethyl)benzene) [47]. The
2
-1
absorption band seen in the range 2968-2862 cm is attributed to the aliphatic ν(C–H)
vibration of the C–H groups of the bisopib and pbisopix ligands. The stretching bands of CO,
6

SO and CNS have been thought as vital bands for the characterization of saccharinate
2
-
1
complexes [50]. The strong and sharp bands at 1663 and 1651 cm are assigned to the
carbonyl group of the sac ligand for complexes 1 and 2, respectively [48]. The strong bands
-1
at 1285, 1269 and 1153, 1150 cm for complexes 1 and 2 correspond to the asymmetric and
symmetric stretches of the SO group, respectively. The asymmetric and symmetric
absorption bands of the CNS moiety of the sac ligand in all the complexes are observed at
2
-1
1
354 and 1340 cm , respectively.
1
0
Luminescent d metal complexes have been evolving and gaining attention [49-51]. The
studies of the photoluminescent properties of Ag(I) complexes reveal that their properties
stem from the metal ions and the ligands coordinated with them [28,29,52]. Due to the
luminescent properties of Ag(I) complexes, the emission spectra of the complexes and the
ligand as NaSac were investigated in the solid state at room temperature (Fig. 1.).
NaSac shows a photoluminescent emission band at 339 nm (λex = 275 nm) [21] upon
excitation at 275 nm, which is attributed to the π*→π and/or π*→n transition [38].
Complexes 1 and 2 show luminescence with an emission band maximum at 422 and 422 nm
and a shoulder at 484 and 477 nm upon excitation at 347 and 346 nm, respectively. The
emissions of the complexes may be attributed to ligand centered luminescence emissions.
Similar emission bands at 420 and 487 nm for [Ag(sac)(Ph
diphenylsulfimide [53] and 427 nm for [Ag (sac) (mpyz) (H O) ] (mpyz = 2-methylpyrazine)
54] have been recently observed.
2
SNH)] (Ph SNH = S,S-
2
4
4
2
2
2
[
3
.2. Crystal structures
The relevant crystal data and experimental conditions with the final parameters are
summarized in Table 2. Details of the interaction distances and geometries are given in Tables
3
-5.
7

3
.2.1. Crystal structure of [Ag(sac)(µ-bisopib)] (1)
The molecular structure of 1, with the atom numbering scheme, is shown in Fig. 2. Selected
bond distances and angles are listed in Table 3. The single X-ray single crystal analysis
reveals that complex 1 crystallizes in the monoclinic space group C2/c and is a one-
dimensional coordination polymer. The asymmetric unit of 1 consists of half an Ag(I) ion,
half a bisopib ligand and half a sac ligand. The Ag(I) ion is located on a center of symmetry
and is coordination by two nitrogen [Ag1-N1=2.282(3) Å] atoms from two different bisopib
ligands and one nitrogen atom [Ag1-N3=2.164(4) Å] from a sac ligand. The bisopib ligand
acts as a bidentate bridging ligand between two Ag(I) centers through the imidazolyl N atoms,
forming a one-dimensional zig-zag chain. The sac ligand acts as a monodentate ligand,
coordinated by the imino nitrogen atom. The Ag1–N1 bond length (2.282(3) Å) is shorter
than the corresponding bond in [and [Ag
bond distance is similar to the corresponding value found in the reported complex
Ag (sac) (µ-pbix) ] (2.172(3) Å) [56]. The coordination sphere of the Ag(I) ion is a trigonal
2
(sac)
2
(µ-aepy)] (2.449(2) Å)[55]. However, this
[
2
2
2
planar coordination geometry. The Ag(I) ions are bridged by bisopib ligands to generate a zig-
zag 1D coordination polymer running parallel to the [101] direction (Fig. 3(a)), with an
Ag···Ag separation of 12.824 Å. It is worth mentioning that the most important structural
property of complex 1 is the presence of very close C-H···Ag(I) interactions between the
Ag(I) and H atoms of the isopropyl groups of the bisopib ligands, as characterized by the
single crystal X-ray studies (Fig. 3(a)). As far as we know, complex 1 shows the closest C-
H···Ag(I) interaction distance among similar literature examples (Table 4). The parameters of
the C-H···Ag(I) interaction between the Ag(I) ion and H atom of the bisopib ligand (Fig. 2)
are: Ag1···H5A 2.63(7) Å; Ag1···C5, 3.427(8) Å; C5-H5A···Ag1, 143.1(2)°. Complex 1 also
contains one π···π interaction. An intermolecular π···π contact occurs between imidazole rings
of neighboring molecules. The distance between the ring centroids is 3.75 Å. Adjacent 1D
8

coordination polymers are further joined by C-H···O hydrogen bonds and π···π interactions,
generating a 3D supramolecular network (Fig. 3(b) and Table 5).
3
2
.2.2. Crystal Structure of [Ag(sac)(µ-bisopix)]·H O (2)
The asymmetric unit of 2 consists of one Ag(I) ion, one bisopix ligand, one sac ligand and a
non-coordinated water molecule (Fig. 4). The Ag(I) ion is coordination by two nitrogen [Ag1-
i
N2A = 2.254(14) Å and Ag1-N5 = 2.184(4) Å] atoms from two different bisopix ligands and
one nitrogen atom [Ag1-N1 = 2.291(4) Å] from the sac ligand, thus showing a trigonal planar
coordination geometry [(i) -x+1, -y+1, -z] (Table 3). The Ag(I) ions are bridged by bisopix
ligands to generate an [Ag
Like complex 1, complex 2 shows a C-H···Ag(I) close interaction (Fig. 4 and Table 4),
Ag1···H26D = 2.74(8) Å, Ag1···C26 = 3.494(8) Å and C26-H26A···Ag1 = 138.4(5)°] and C-
H···π interactions. The C-H···π interactions occur between the bisopix and sac ligands. Details
of these interactions are presented in Table 3. The [Ag (bisopix) (sac) ] clusters are joined by
2 2 2
(bisopix) (sac) ] cluster, with an Ag···Ag separation of 10.295 Å.
[
2
2
2
C-H···π interactions, generating a 2D network (Fig. 4). The C-H···O hydrogen bonds and C-
H···π interactions play a crucial role in the architecture of the 3D network (Fig. 5. and Table
5
).
3
.3 Structural comparison
Within the scope of this study, bis(imidazole) derivatives ligands containing isopropyl groups
were preferred to examine C–H···Ag interactions. In addition, the carbon skeletons of the
ligands including isopropyl groups at the ends were selected considering them as flexible and
semi-flexible. The reason for this choice was to examine the effect of the flexibility of these
groups on the final supramolecular structure. Complex 1, containing the bisopib ligand with a
flexible aliphatic -(CH
2
4
) - carbon skeleton, exhibited a 1D zig-zag structure. In addition, very
close C–H···Ag interactions were observed in complex 1. Complex 2 has the bisopix ligand,
9

which has a semi-flexible xylene carbon skeleton. Complex 2 has a dinuclear structure
because the semi-flexible groups do not rotate enough to form polynuclear complexes.
3
.4. Thermal analysis
To study the thermal stabilities of the synthesized complexes, thermal analyses (TG, DTG and
DTA) were performed on the as-synthesised single crystal samples (Fig. S2 and S3.).
[
Ag(sac)(µ-bisopib)] (1) melts at 201 °C and begins to decompose at 213 °C. The thermal
decomposition of 1 occurs in two steps. It is hard to understand the decomposition steps
owing to a continuous mass loss, as seen in the TG curve of 1. The weight loss of 81.17% in
the region 213-622 °C corresponds to the elimination of one bisopib and one sac ligand for 1
(
calculated: 80.88% and DTGmax. = 360.60 and 592.42 °C for 1). Final product for 1 was
calculated as metallic silver [57].
The first stage between 106 and 116 ºC for [Ag(sac)(µ-bisopix)]·H
endothermic elimination of one water molecule, with an experimental mass loss of 3.67%
calcd. mass loss 2.85%). The second stage, between 116 and 332 ºC, is related to elimination
2
O (2) corresponds to the
(
of one bisopix ligand (DTGmax.= 346.45 °C, found 51.54%, calcd. 51.14%). The last stage,
between 322 and 440 ºC, is related to the decomposition of the sac ligand, with an exothermic
effect (DTGmax.= 551 ºC, found 26.25 %, calcd. 26.36 %). The remaining mass of 18.54% is
metallic Ag, which is compatible with the calculated value of 19.65%.
4
. Conclusion
Two bis(isopropylimidazole) derivative ligands and their complexes with the Ag(I) ion were
synthesized. The results showed that the different aromatic and aliphatic groups inserted on
the backbone of the bis(isopropylimidazole) ligands did affect the structures of the
synthesized complexes. Crystal analysis showed that complex 1 had a polynuclear structure,
whereas complex 2 had a dinuclear structure. The thermal stabilities increased on changing to
aromatic groups from aliphatic substitute groups on the imidazole rings. Photoluminescence
10

spectra of the complexes showed that complex 1 exhibited a more intense emission compared
to complex 2, which could stem from close aromatic interactions between the imidazole rings
in complex 1.
5
. Supplementary material
Fig. S1. shows the IR spectra of complexes 1 and 2. Figs. S2 and S3. exhibit the TG, DTA
and DTG curves for 1 and 2, respectively.
Acknowledgements
The authors acknowledge the Scientific and Technological Research Application and
Research Center, Sinop University, Turkey, for the use of the Bruker D8 QUEST
diffractometer.
Appendix A. Supplementary data
CCDC 1487363 and 1487364 contain the supplementary crystallographic data for 1 and 2.
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.
Scheme 1. Bis(isopropyl)imidazole ligands containing aromatic and aliphatic backbones
11

Table 1. Crystal data and structure refinement parameters for complexes 1 and 2.
Crystal data
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
1
2
C
23
H
30
N
5
O
3
SAg
C
54
H
64
N
10
O
8
S
2
Ag
2
564.45
1261.01
Monoclinic
C2/c
Triclinic
P-1
15.237(5)
13.438(4)
13.463(5)
90.00
10.4523(9)
10.5654(9)
14.9466(2)
105.731(4)
98.631(5)
96.425(4)
1550.50(2)
1
b (Å)
c (Å)
α (º)
β (º)
114.43(2)
90.00
γ (º)
3
V (Å )
2509.90(2)
4
Z
-
3
D
c
(g cm )
1.494
1.351
-1
µ (mm )
0.92
0.76
θ range (º)
3.0-28.3
39933
3.0-24.0
66267
Measured refls.
Independent refls.
3131
6070
R
int
0.034
0.053
S
1.05
1.07
R1/wR2
0.056/0.132
1.07/-1.44
0.060/0.199
1.87/-0.50
-
3
∆ρmax/∆ρmin (eÅ )
12

Table 2. Selected FT-IR spectral data for [Ag(sac)], [Ag
complexes 1 and 2 (cm )
2
(sac)
2
(o-bix) ], together with
2
-1
Assignment
ν(CH)aliphatic
ν(CO)
[Ag(sac)]
[Ag
2
(sac)
2
(o-bix)
2
]
{[Ag(sac)(µ-
bisopib)]} (1)
2955m, 2922m, 2862m 2968m, 2930m,
866m
[Ag(sac)(µ-
[
-
46]
[47]
-
n
pbisopix)] ·2H O (2)
2
2
2
1640sh,
612vs
1639vs
1663vs
1651vs
1
ν(CC)
1577vs, 1458s
1338sh
1583vs, 1454m
1328sh
1592m
1354sh
1285vs
1587m
1340sh
1269vs
ν
ν
s
(CNS)
as(SO
2
)
1284vs,
1251vs
1
258vs
ν
s
(SO
2
)
1150vs
1147vs
1153vs
1150vs
Sh = shoulder; w = weak; m = medium; s = strong; vs = very strong.
13

Table 3. Selected bond distances and angles for complexes 1 and 2 (Å, º)
Complex 1
N3-Ag1
2.164(4)
N1-Ag1
2.282(3)
i
N3-Ag1-N1
136.29(7)
N1-Ag1-N1
87.42(15)
Complex 2
Ag1-N1
2.291(4)
2.184(4)
102.0(3)
120.68(15)
Ag1-N2A
2.254(14)
137.3(3)
i
Ag1-N5
i
N2A-Ag1-N1
N5 -Ag1-N2A
i
N5 -Ag1-N1
Symmetry codes: (i) -x+1, y, -z+3/2 for 1; (i) -x+1, -y+1, -z for 2.
14

Table 4. Interaction distances (Å) and angles (°) for selected Ag(I) complexes, including
close C-H···Ag(I) interactions
Complexes
d[Ag(I)··· H]
2.630
d[Ag(I)···C]
3.427
a[C-H···Ag(I)]
143.12
Ref
1
2
This work
This work
[27]
2,715
3,496
138.94
[Ag
2
L1](ClO
4
)
2
2.944
3.475
109.0
[
Ag6(L2)
Ag (µ-2,3-
(Hpda)
[AgL3](ClO
Ag (µ -sac) (µ-nmpen)]
6
(dmp)
2
]
2.823
2.811
3.541
3.232
134.24
106.25
[28]
[29]
[
2
pydc)
2
2
]⋅2H
)}
2
O
{
4
2
2.657
2.684
3.198
3.275
116.60-
119.71
[30]
[31]
[
2
3
2
n
[
L1 = hexakis(3-(2-pyridyl)pyrazol-1-ylmethyl)benzene; HL2; anthracene-9-carboxylic acid,
= pyridine-2,3-dicarboxylic acid; pda = 1,3-
dmp = 2,6-dimethylpyridin; 2,3-pydcH
2
diaminopropane; L3 = 9-[3-(2-pyridyl)pyrazol-1-yl]- acridine; sac = saccharinate; nmpen =
N-methyl-1,3-propanediamine]
15

Table 5. Hydrogen-bond parameters for complexes 1-2 (Å, º)
D-H· · ·A
D-H
H···A
D···A
D-H···A
Complex 1
iii
iii
C2—H2···O1
C2—H2···O3
0.93
0.93
0.97
0.97
2.46
2.37
2.53
2.55
3.385(6)
3.221(6)
3.217(7)
3.159(10)
174
153
128
121
iii
C7—H7A···O2
iii
C8—H8B···O2
Complex 2
ii
C22—H22···O1
0.93
2.60
3.472(7)
3.537(9)
3.169(13)
2.725(12)
3.945(3)
3.901(4)
156
177
168
145
136
146
iii
C14—H14B···O1
0.97
2.57
iv
C9A—H9A···O2
0.93
2.25
i
O4—H4A···O3
0.84(1)
0.93
2.00(3)
3.21
iv
C2—H2···Cg(1)
C27—H27B···Cg(1)
v
0.96
3.06
Symmetry codes: (iii) x, −y+1, z−1/2 for 1; (i) −x+1, −y+1, −z; (ii) x+1, y+1, z; (iii) x, y+1, z;
iv) −x+1, −y+1, −z+1; (v) 1-x, 2-y, -z; Cg(1)=C15-C20; for 2.
(
16

NaSac
Intensity (a.u.)
Complex 1
Complex 2
300
350
400
450
500
550
600
Wavelength [nm]
Fig 1. Solid state room temperature emission spectra of Na(sac), together with complexes 1
and 2
17

Fig. 2. The molecular structure of 1 showing the atom numbering scheme. [(i) -x+1, y, -z+3/2;
ii) -x+1/2, -y+1/2, -z+1]
(
18

(
a)
(
b)
Fig. 3. (a) Zig-zag 1D polymer of 1 with the C-H···Ag(I) interactions. (b) 3D supramolecular
network of 1.
19

Fig. 4. The molecular structure of 2 showing the atom numbering scheme. [(i) -x+1, -y+1, -z]
Fig. 5. An infinite 2D layer in 2.
20

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22

Graphical abstract
-
n 2
[Ag(sac)(µ-bisopib)] (1) and [Ag(sac)(µ- bisopix)]·H O (2) have been synthesized based on
bis(isopropylimidazole) ligands
-
Complex 1 shows the closest C-H···Ag interaction distance among similar literature
examples
-
The C-H···O hydrogen bonds and C-H···π interactions play a crucial role in the architecture
of the 3D network of complex 2
2
3