Molar-ratio-dependent supramolecular isomerism: AgI coordination polymers with bis(cyanobenzyl)sulfides

Article abstract of DOI:10.1002/chem.201302633

The ratio is the key: On varying the molar ratio of the reactants, AgNO₃ and tridentate m-L ligand, supramolecular isomers 1 and 2 comprising a 2D polymeric network were obtained. Conformational differences of m-L play a crucial role in the 2D network structures adopted for isomers 1 and 2. Copyright

Full text of DOI:10.1002/chem.201302633

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DOI: 10.1002/chem.201302633
Molar-Ratio-Dependent Supramolecular Isomerism: AgI Coordination
Polymers with Bis(cyanobenzyl)sulfides
Eunji Lee, Ja-Yeon Kim, Shim Sung Lee,* and Ki-Min Park*[a]
Chem. Eur. J. 2013, 00, 0 – 0
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Supramolecular isomerism has received increasing atten-
tion in the area of molecular and crystal engineering, since
Zaworotko first coined the term “supramolecular iso-
mers”.[1] Such isomers correspond to different supramolecu-
lar structures constructed from the same molecular building
blocks, giving rise to structural isomerism at the supramolec-
ular level—a range of papers concerned with supramolecu-
lar isomerism have now appeared in the literature.[2–9] In this
context, refining the synthetic procedures used to produce
supramolecular isomers is important, since it provides an
opportunity for gaining a better understanding of the factors
that influence the formation of individual isomer structures.
There have been a number of studies focused on under-
standing the factors leading to supramolecular isomerism.
Until now, factors such as temperature,[3] choice of solvent,[4]
the presence of a template[5] or guest,[6] pH,[7] catenation[8]
or concentration[9] have all been shown to affect the self-as-
sembly of particular supramolecular isomers.
was investigated; comparative studies for o-L and p-L were
also carried out.
Overall we have been successful in isolating four silver(I)
coordination polymers (1–4) with different topologies from
the reaction of AgNO3 with o-L, m-L and p-L. Indeed, an
intriguing feature of the results is the observation of molar-
ratio-dependent supramolecular isomerism (or conforma-
tional polymorphism) in the formation of the 2D coordina-
tion polymers obtained with m-L (isomers
1 and 2,
Scheme 1). The conformational difference adopted by m-L
Over recent years our group has investigated the use of li-
gands incorporating sulfur donors in conjunction with aro-
matic backbone unit on the structural diversity often ob-
served in the resulting discrete and infinite supramolecular
product obtained from such systems.[10] In the present study
the three regioisomers of bis(cyanobenzyl)sulfide (o-L, m-L,
and p-L) were chosen as organic building blocks for assem-
bly reactions with thiaphilic AgNO3.
Scheme 1. Molar-ratio-dependent supramolecular isomers 1 and 2 show-
ing the conformational differences of m-L in each.
These ligands are somewhat flexible due to free rotation
À
À
around the C S and C C bonds, and this appeared likely to
induce structural diversity across their respective com-
has been probed by single-crystal X-ray analysis. Powder X-
ray diffraction (PXRD) analysis has also been applied to
monitor the observed molar-ratio-dependent supramolecular
isomerism. To the best of our knowledge, supramolecular
isomerism of this type has not been reported previously for
network complexes.
The ligands o-L, m-L and p-L were synthesised by the re-
action of sodium sulfide and the corresponding bromometh-
yl benzonitrile derivative in methanol–water (7:3 v/v) (Sup-
porting Information); the synthesis of p-L from the reaction
of p-cyanobenzyl mercaptan and p-cyanobenzyl chloride has
also been previously reported by Barkenbus et al.[12]
For the synthesis of 1–4, the concentration of AgNO3 was
varied relative to the ligand concentration in order to exam-
ine the effect of reactant molar ratio on the nature of the re-
sulting complexes. Notably, this approach enabled us to iso-
late the supramolecular isomers of 1 and 2 incorporating m-
L (Scheme 1). The individual isomer structures and connec-
tivity patterns were found to be reflected by the ligand con-
formations as depicted in Scheme 1. Under identical reac-
tion conditions to the above, o-L and p-L solely yielded the
respective products 3 and 4; that is, no molar-ratio depend-
ency was observed in either case.
plexes.[11] For example, on coordination of a soft metal ion
to their sulfur donors, o-L and p-L might be expected to
favour metallocyclic and linear products, respectively (when
the coordination vectors associated with the positions of the
terminal cyano groups are considered). In contrast, reflect-
ing its intermediate nature of m-L between o-L and p-L, it
is difficult to predict the likely coordination behaviour. For
this ligand system we have investigated whether minor fac-
tors such as the molar ratio of the reactants (that is, the
metal-to-ligand ratio) might be employed to control the
nature of the resulting complex type. Based on this assump-
tion, we performed a systematic series of experiments in
which the effect of changing the molar ratio of the metal
salt to ligand in the syntheses of AgNO3 complexes of m-L
[a] E. Lee, J.-Y. Kim, S. S. Lee, K.-M. Park
Department of Chemistry and Research Institute of Natural Science
Gyeongsang National University, Jinju 660-701 (Republic of Korea)
E-mail: sslee@gsnu.ac.kr
Preparation and structural comparison of supramolecular
isomers (1 and 2): Direct mixing of a solution of m-L in di-
chloromethane with one equivalent of AgNO3 in methanol
and allowing the solution to evaporate at room temperature
afforded 1 as a colourless crystalline product. As mentioned
above, when a large excess of AgNO3 (above ten equiva-
kmpark@gnu.ac.kr
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201302633.
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Supramolecular Isomerism
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lents) was reacted with m-L, 2 was obtained as colourless
crystals. Single-crystal X-ray analysis confirmed that 1 and 2
are supramolecular isomers with the composition [Ag2-
ure 1b and c). That is, the single block unit of 1 is a simple
20-membered metallocycle {Ag6ACHTNUGTREN(UNG NO2)4S2}, in which six Ag
À
atoms are linked by four m2-NO3 units and two sulfur
donors. The association of the single block unit in the her-
ringbone arrangement generates the neutral puckered 2D
network 1. Similar to isomer 1, the 2D network of isomer 2
ACHTUNGTRENNUNG(m-L)ACHTUNGTRENNUNG(NO3)2]n. Both feature 2D polymeric arrangements
(Figures 1 and 2). Comparison of the PXRD patterns for the
synthesised products with the simulated patterns for isomers
1 and 2 confirmed that the isolated samples were phase pure
(see Figure 3, below).
À
is made up of 1D (Ag NO3)n zigzag backbones. These inor-
ganic backbones are further cross-linked by m-L units by
À
À
Isomer 1 crystallised in the monoclinic space group P21
with Z=2. The asymmetric unit contains one molecule of
m-L, two Ag atoms, and two NO3 moieties. The two Ag
means of Ag S and Ag N bonds to give a distorted honey-
comb-like 2D network. Isomer 2 also has a (6,3) net topolo-
gy and Ag atoms provide the three-connected nodes (Fig-
ure 2b,c). So, in general, the connectivity pattern and the
composition of the single block unit in 2 is almost identical
to that in 1.
À
atoms (Ag1 and Ag2, Figure 1a) show similar coordination
environments. Each Ag centre is four-coordinate, being
bound to one cyano nitrogen atom from one m-L, one sulfur
À
atom from an adjacent m-L, and two monodentate NO3
The most striking difference between the two isomers lies
in the conformation of m-L, which acts as a tridentate
ligand in each case. For example, m-L in 1 is fully “stretch-
ed” and its two cyano groups are oriented away from each
other to form an “S”-shaped configuration (Figure 1d). So,
the three consecutive block units in 1 contain one m-L mol-
ions. The coordination geometry around each Ag atom in 1
is distorted tetrahedral, with the “tetrahedral” angles falling
in the range 91.8(1)–127.1(1)8 for Ag1 and 88.8(1)–123.7(1)8
for Ag2. Isomer 2 crystallised in the monoclinic space group
C2/c with Z=4. The asymmetric unit contains a half-mole-
À
cule of m-L, one Ag atom, and one NO3 ion, since m-L is
ecule with
a
trans–gauche–gauche–trans arrangement
À
located on a two-fold rotation axis. The Ag atom in this
isomer is also four-coordinate and its local coordination en-
vironment (85.2(1)–133.1(1)8) is similar to that of the Ag
atom in isomer 1 (Figure 2a).
In isomer 1, Ag atoms are linked by m2-NO3 to form a
1D zigzag backbone, with further cross-linking by m-L
through two Ag-N and one Ag S bonds. A single block unit
in isomer 2 holds one m-L molecule with a “V”-shape and a
gauche–gauche–gauche–gauche arrangement through two
À
À
Ag N bonds and one Ag S bond (Figure 2d). Accordingly,
the length of m-L (N1···N1C 7.46 ꢁ) in 2 is much shorter
than that in isomer 1 (N1···N2 12.49 ꢁ).
À
À
À
(through Ag S and Ag N bonds) to form a 2D layer.
Isomer 1 has a (6,3) net topology, in which Ag atoms pro-
vide the three-connected nodes to yield a herringbone pat-
tern with a rectangular window as a single block unit (Fig-
In the packing structure, the 2D sheets in 1 are stacked
À
with weak C H···O hydrogen bonds (2.55 and 2.43 ꢁ,
dashed lines in Figure 1e) with interlayer separation of half
the a-axial length (10.123 ꢁ). The structure of 2 (Figure 2b)
Figure 1. Crystal structure of isomer 1, [Ag2ACHTNUTRGENN(UG m-L)ACHTUNGTNER(NUNG NO3)2]n: a) basic coordination unit, b) 2D layered network, c) herringbone pattern (ligands are omit-
ted except for sulfur atoms), d) “S”-shape ligand conformation showing the trans-gauche-gauche-trans arrangement in three consecutive block units, and
À
e) packing arrangement showing interlayer C H···O hydrogen bonds.
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S. S. Lee, K.-M. Park et al.
Figure 2. Crystal structure of isomer 2, [Ag2ACHTNUTRGENN(UG m-L)ACHTUNGTNER(NUNG NO3)2]n: a) basic coordination unit, b) 2D layered network, c) distorted honeycomb pattern (ligands
are omitted except for sulfur atoms), d) “V”-shape ligand conformation showing the gauche–gauche–gauche–gauche arrangement in a single block unit,
À
and e) packing arrangement showing interlayer C H···O hydrogen-bonds and p–p interactions.
À
is also reinforced by interlayer interactions by weak C
H···O hydrogen bonds (2.60 and 2.63 ꢁ, dashed lines in Fig-
ure 2e) as well as by p···p stacking interactions (centroid···-
centroid 3.75 ꢁ) with the interlayer separation half of the c-
axial length (9.145 ꢁ).
any existing isomer 1 is converted into isomer 2 with an as-
sociated conformational change of m-L from the “S”- to the
“V”-shape as already discussed (Figure 1d and 2d). Hence,
The different structures observed for 1 and 2 are reflected
in the conformational differences of the m-L ligand in each
product. To the best of our knowledge, this is the first exam-
ple of supramolecular isomers based on conformational
ligand changes that are induced by a molar-ratio variation of
the reactants employed for their synthesis.
PXRD study of supramolecular isomers (1 and 2): Our sys-
tematic studies in which the reactant molar ratios were
varied to give supramolecular isomerism were monitored by
the determination of consecutive PXRD patterns of each of
the isolated products. The PXRD patterns of the products
obtained for each molar ratio are shown in Figure 3 together
with the simulated PXRD patterns for 1 and 2 derived from
the corresponding single-crystal X-ray analysis data. For a
molar ratio in the range 1.0–5.0, the PXRD patterns of the
respective products match well with the simulated pattern
for isomer 1, indicating that this is the only product formed
in this region. When the ratio is in range 5.0–10, additional
peaks were observed, that suggested the presence of a mix-
ture of isomers 1 and 2. On increasing the molar ratio above
10, the peaks for isomer 1 disappeared and only those for
isomer 2 were then present. Thus, it can be concluded that
as the content of AgNO3 in the reaction solution increases,
Figure 3. PXRD patterns of the products by varying the reactant mole
ratios (AgNO3/m-L=1-20 equiv). Bottom and top data represent the si-
mulated PXRD patterns of isomer 1 and isomer 2, respectively, based on
single-crystal X-ray analysis.
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Supramolecular Isomerism
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the combined approach of
single-crystal X-ray analysis and
PXRD pattern analysis has ena-
bled in-depth information con-
cerning the control of supramo-
lecular isomerism through reac-
tant molar ratio variation.
The reversibility between
isomer 1 and isomer 2 were ex-
amined by analysing the recrys-
tallised products with PXRD
patterns (Figure S1 in the Sup-
porting Information). When
isomer 1 was immersed in a
methanol
containing
10–
20 equivalents of AgNO3 for
24 h, isomer 1 was maintained
without change. On the other
hand, when isomer 2 was im-
mersed in a pure methanol sol-
Figure 4. Crystal structure of 3, [AgACTHUNGTRENNNUG
in 1D looped chain, and c) interchain p–p interactions and C H···O type hydrogen bonds.
À
vent for 24 h, the conversion to isomer 1 by recrystallisation
was confirmed. According to the observed irreversibility, it
is concluded that isomer 1 with the “S”-shaped ligand con-
formation is thermodynamically more stable than isomer 2
with the “V”-shaped ligand conformation. The role of the
excess amount of AgNO3 on the conformational change is
one of the core phenomena in this work. However, it is not
easy to explain or predict such behaviour in the high con-
centrated electrolyte solution, because the ionic species act
in a similar fashion as the solvent (medium effect).[13]
around Ag1 is distorted tetrahedral, with the “tetrahedral”
angles falling in the range 78.53(6)–131.42(5)8. The large dis-
tortion is presumably largely caused by the formation of the
12-membered metallocycle incorporating a presumably rigid
CN-Ag-NC bond angle. In the crystal packing (Figure 4c),
each 1D loop-chain is aligned side by side and these inter-
acts by the offset face-to-face p–p stacking; the intercent-
À
roid distance is 3.93 ꢁ. C H···O interchain hydrogen bonds
are also present.
On reaction with AgNO3, p-L forms the multichannel 3D
framework 4 with the formula [Ag2ACHTUNGTRENNUG(p-L)AHCTUNTGERN(NUGN NO3)2]n (Figure 5).
AgI coordination polymers of o-L and p-L (3 and 4): In ad-
dition to the m-L complexes with AgNO3 just discussed, the
ortho (o-L) and para (p-L) ligands were also employed in a
similar series of experiments in order to probe the possible
molar-ratio dependency for these two ligand systems. As
mentioned already, when the intrinsic coordination vectors
for o-L and p-L are considered then metallocyclic and a
linear complex product, respectively, might be expected to
form. We found no dependence on the molar ratio of the re-
actants in each of these cases. This conclusion was also vali-
dated by the corresponding variable-molar-ratio PXRD pat-
terns for these two ligand systems (Figure S2 in the Support-
ing Information).
The product 4 crystallised in the monoclinic space group C2/
c with Z=4. The asymmetric unit contains a half-molecule
of p-L located on a twofold axis, one Ag atom, and one
À
NO3 ligand. The Ag atom is five-coordinate, being bound
to one cyano nitrogen atom from one p-L and one sulfur
atom of from another p-L. The coordination sphere is com-
pleted by three oxygen atoms from two nitrate anions,
adopting mono- and bidentate bridging modes, respectively,
that link two Ag centres (Ag1···Ag1B, 3.89 ꢁ). Effectively,
the two halves of each ligand connect two Ag atoms to gen-
erate a looped chain, with the sulfur nodes defining a helical
arrangement (Figure 5b). The helix-like channels are further
doubly connected by the nitrate ions, resulting in a 3D mul-
tichannel framework. Notably, the conformation of p-L has
an elongated “M”-shape with its two cyano groups directed
to opposite sides and being bound to Ag atoms in two
neighbouring repeat units. Thus, the length of p-L in 4
(N1···N1C 14.44 ꢁ) is much greater than that of o-L in 3
(N1···N2 3.50 ꢁ).
Reaction of o-L with AgNO3 afforded 3 as colourless
crystals of formula [AgACHTNUTRGNE(NUG o-L)NO3]n. This product has an in-
finite 1D looped chain structure. Product 3 crystallised in
the monoclinic space group P21/c with Z=4. The asymmet-
ric unit contains one molecule of o-L, one Ag atom, and
À
one NO3 . The Ag atom is four-coordinate, being bound to
two cyano nitrogen atoms from one o-L and one sulfur
It is notable that 4 features a 3D polymeric arrangement
donor from an adjacent ligand to form the looped chain
of formula [Ag2ACTHNGUTRENNU(G p-L)ACHTUNGTRNE(NUNG NO3)2]n. Even though its formula is
(Figure 4). The coordination sphere is completed by an O
similar to that of 1 and 2, its structure differs markedly un-
doubtedly reflecting the preferred conformations of the re-
spective ligand isomers.
À
atom from NO3 bound in
a monodentate manner
(Ag1···O2 2.920(2) ꢁ, Figure 4a). As anticipated, two cyano
À
N atoms in o-L are linked by one m2-Ag atom through Ag
N bonds to form a metallocycle. The coordination geometry
In conclusion, three regioisomers of bis(cyanobenzyl)sul-
fide have been synthesised and their 1D and 3D silver(I) ni-
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S. S. Lee, K.-M. Park et al.
Figure 5. Crystal structure of 4, [Ag
2ACHTUNGTREN(GUN p-L)ACHTUGNTERN(NUGN NO3)2]n: a) basic coordination unit, b) closer views of one channel unit of the multichannel type 3D structure
(top view and side view), c) elongated “M”-shape ligand conformation, d) top view of the multichannel, and e) side view of the multichannel.
trate coordination polymers isolated and structurally charac-
terised. Systematic investigation of these network complexes
clearly shows that m-L gives rise to two 2D supramolecular
isomers incorporating different conformations of the bound
ligand. Formation of these isomers is dependent on the
molar ratio of the reactants used for their synthesis. For o-L
and p-L, however, variation of the metal-to-ligand ratio
yielded identical products for each ligand across all molar
ratios employed. The present study demonstrates that both
the choice of particular semi-flexible ligand isomers of the
present type as well as the variation of the molar ratio of re-
actants used for complex synthesis can each play an impor-
tant role in influencing the structures of the corresponding
frameworks generated in each case.
Experimental Section
General: All chemicals and solvents used in the syntheses were of re-
agent grade and were used without further purification. NMR spectra
were recorded on a Bruker 300 spectrometer (300 MHz). The FT-IR
spectra were measured with a Nicolet iS10 spectrometer. The ESI-mass
spectra were obtained on a Thermo Scientific LCQ Fleet spectrometer.
Each product obtained in this work was dried in a vacuum before ele-
mental analysis, which was carried out on a Thermo Scientific Flash 2000
Series elemental analyser. Thermogravimetric analyses were recorded in
a TA Instruments TGA-Q50 thermogravimetric analyser. Samples were
heated at a constant rate of 58C minÀ1 from room temperature to 9008C
in a continuous-flow nitrogen atmosphere. The powder X-ray diffraction
(PXRD) experiments were performed in a transmission mode with a
Bruker GADDS diffractometer equipped with graphite monochromated
CuKa radiation (l=1.54073 ꢁ).
Synthesis and characterisation of o-L: A solution of Na2S (0.6 g, 0.007
mol) in water (30 mL) was added to a stirred solution of 2-(bromome-
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thyl)benzonitrile (3.0 g, 0.015 mol) in ethanol (45 mL) in a round-bot-
tomed flask. The resulting solution was stirred at room temperature for
2 h, the ethanol was evaporated, and the residue was partitioned between
water and dichloromethane. The combined organic layers were dried
over anhydrous sodium sulfate and evaporated to dryness. The flash
column chromatography (SiO2; ethyl acetate/n-hexane 1:9) afforded the
product as a pale-yellow solid in 60% yield. M.p. 115–1168C; 1H NMR
(300 MHz, CDCl3): d=7.34–7.65 (m, 8H; Ar), 3.91 ppm (s, 4H;
ArCH2S); 13C NMR (75 MHz, CDCl3): d=141.5, 133.1, 133.0, 130.0,
127.8, 117.4, 112.7, 34.5 ppm; IR (KBr): n˜ =3057, 2969, 2936, 2233, 2222,
1594, 1490, 1473, 1446, 1402, 1300, 1247, 865, 770, 755, 704 cmÀ1; MS
(ESI): m/z: 287.15 [C16H12N2S1 +Na]+; elemental analysis calcd (%) for
C16H12N2S1: C 72.70, H 4.58, N 10.60, S 12.13; found: C 72.86, H 4.51, N
10.84, S 12.30.
X-ray crystallographic analysis: All data were collected
on a Bruker SMART APEX II ULTRA diffractometer
equipped with graphite monochromated MoKa radiation
(l=0.71073 ꢁ) generated by a rotating anode. The cell pa-
rameters for the compounds were obtained from a least-
squares refinement of the spot (from 36 collected frames).
Data collection, data reduction, and semi-empirical absorp-
tion correction were carried out using the software package
of APEX2.[14] All of the calculations for the structure deter-
mination were carried out using the SHELXTL package.[15]
In all cases, all non-hydrogen atoms were refined anisotropi-
cally and all hydrogen atoms were placed in idealised posi-
tions and refined isotropically in a riding manner along with
the their respective parent atoms. Relevant crystal data col-
lection and refinement data for the crystal structures of 1–4
are summarised in Table S1 in the Supporting Information.
CCDC-943501 (1), CCDC-943502 (2), CCDC-943503 (3),
and CCDC-943504 (4) contain the supplementary crystallo-
graphic 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.
Synthesis and characterisation of m-L: The procedure was the same as
for o-L, but with the use of 3-(bromomethyl)benzonitrile. The purifica-
tion of the product, was also slightly different; it was recrystallised from
1
dichloromethane/n-hexane (1:30). Yield: 65%; m.p. 103–1048C; H NMR
(300 MHz, CDCl3): d=7.27–7.57 (m, 8H; Ar), 3.63 ppm (s, 4H;
ArCH2S); 13C NMR (75 MHz, CDCl3): d=139.3, 133.3, 132.3, 131.0,
129.4, 118.5, 112.8, 35.3 ppm; IR (KBr): n˜ =3075, 2934, 2228, 1595, 1577,
1478, 1429, 1418, 1225, 1083, 899, 825, 809, 728, 704, 684 cmÀ1; MS (ESI):
m/z: 287.08 [C16H12N2S1 +Na]+; elemental analysis calcd (%) for
C16H12N2S1: C 72.70, H 4.58, N 10.60, S 12.13; found: C 72.84, H 4.55, N
10.88, S 12.35.
Synthesis and characterisation of p-L: The procedure was same as for
m-L, but with the use of 4-(bromomethyl)benzonitrile; the synthesis of
p-L has also been reported in the literature.[12] Yield: 60%. 13C NMR
(75 MHz, CDCl3): d=143.2, 132.5, 132.4, 129.7, 129.1, 118.6, 111.2,
35.5 ppm; IR (KBr): n˜ =3051, 3033, 2925, 2229, 1602, 1501, 1421, 1172,
1102, 915, 852, 809, 758, 1364, 1222, 1103, 1001, 801 cmÀ1; MS (ESI): m/z:
287.17 [C16H12N2S1 +Na]+; elemental analysis calcd (%) for C16H12N2S1:
C 72.70, H 4.58, N 10.60, S 12.13; found: C 72.84, H 4.55, N 10.88, S
12.32.
Acknowledgements
This work was supported from NRF (2010-0022675 and
2012R1A4A1027750). E.L. acknowledges the support by NRF-2013-Fos-
tering Core Leaders of the Future Basic Science Program.
Preparation of 1, [Ag
0.038 mmol) in methanol (2 mL) was added to
2ACHUTGTNERNNUG(m-L)ACHTUGNTRENNNUG
Keywords: crystal engineering · isomers · networking ·
silver · supramolecular chemistry
a
(10.0 mg, 0.038 mmol) in dichloromethane (2 mL). Slow evaporation of
the solution afforded a colourless crystalline product 1 suitable for X-ray
analysis. M.p. 194–1968C; IR (KBr pellet): n˜ =3055, 2936, 2250, 2231,
1599, 1578, 1480, 1298, 1137, 1084, 1033, 904, 832, 807, 746, 709 cmÀ1; ele-
mental analysis calcd (%) for C16H12Ag2N4O6S1: C 31.81, H 2.00, N 9.27,
S 5.31; found: C 31.88, H 1.78, N 9.03, S 5.03.
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b) M.-L. Tong, S. Hu, J. Wang, S. Kitagawa, S. W. Ng, Cryst. Growth
Des. 2005, 5, 837–839; c) P. Kanoo, K. L. Gurunatha, T. K. Maji,
Cryst. Growth Des. 2009, 9, 4147–4156.
Preparation of 2, [Ag2ACTHNUTRGNEN(UG m-L)AHCTUNTGREN(NUNG NO3)2]n: Silver(I) nitrate (64.5 mg,
0.76 mmol) in methanol (2 mL) was added to a solution of m-L (10.0 mg,
0.038 mmol) in dichloromethane (2 mL). Slow evaporation of the solu-
tion afforded a colourless crystalline product 2 suitable for X-ray analysis.
M.p. 194–1968C; IR (KBr pellet): n˜ =3076, 2937, 2361, 2340, 2246, 2229,
1579, 1479, 1385, 1297, 1225, 1172, 1089, 1037, 899, 810, 703 cmÀ1; ele-
mental analysis calcd (%) for C16H12Ag2N4O6S1: C 31.81, H 2.00, N 9.27,
S 5.31; found: C 31.91, H 1.94, N 9.28, S 5.61.
Preparation of 3, [AgACHTUNGTRENNUNG(o-L)NO3]n: Silver(I) nitrate (6.5 mg, 0.038 mmol)
[4] a) T. H. Kim, J. Seo, K.-M. Park, S. S. Lee, J. Kim, Inorg. Chem.
Commun. 2007, 10, 313–317; b) X. C. Huang, D. Li, X. M. Chen,
CrystEngComm 2006, 8, 351–355; c) I. S. Lee, D. M. Shin, Y. K.
Chung, Chem. Eur. J. 2004, 10, 3158–3165; d) X.-C. Huang, J.-P.
Zhang, Y.-Y. Lina, X.-M. Chen, Chem. Commun. 2005, 2232–2234;
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Quesada, Chem. Commun. 2005, 5864–5866.
[5] a) J.-P. Zhang, S. Kitagawa, J. Am. Chem. Soc. 2008, 130, 907–917;
b) Y. Jia, H. Li, Q. Guo, B. Zhao, Y. Zhao, H. Hou, Y. Fan, Eur. J.
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[6] a) I.-H. Park, S. S. Lee, J. J. Vittal, Chem. Eur. J. 2013, 19, 2695–
2702; b) S. Aitipamula, A. Nangia, Chem. Eur. J. 2005, 11, 6727–
6742.
in methanol (2 mL) was added to a solution of o-L (10.0 mg, 0.038 mmol)
in dichloromethane (2 mL). Slow evaporation of the solution afforded a
colourless crystalline product 3 suitable for X-ray analysis. M.p. 169–
1718C; IR (KBr pellet): n˜ =3071, 2978, 2242, 1596, 1487, 1452, 1382,
1322, 1304, 1241, 1159, 1036, 962, 828, 788, 768 cmÀ1; elemental analysis
calcd (%) for C16H12AgN3O3S1: C 44.26, H 2.79, N 9.68, S 7.38; found: C
44.19, H 2.70, N 9.76, S 7.61.
Preparation of 4, [Ag2ACTHNUTRGNEN(UG p-L)AHCTUNTGREN(NUNG NO3)2]n: Silver(I) nitrate (6.5 mg,
0.038 mmol) in methanol (2 mL) was added to a solution of p-L (10.0 mg,
0.038 mmol) in dichloromethane (2 mL). Slow evaporation of the solu-
tion afforded a colourless crystalline product 4 suitable for X-ray analysis.
M.p. 211–2138C; IR (KBr pellet): n˜ =3035, 2974, 2252, 2226, 1604, 1504,
1438, 1423, 1384, 1280, 1235, 1025, 869, 830, 812, 759 cmÀ1; elemental
analysis calcd (%) for C16H12Ag2N4O6S1: C 31.81, H 2.00, N 9.27, S 5.31;
found: C 31.75, H 1.91, N 9.30, S 5.50.
[7] L. Fan, X. Zhang, Z. Sun, W. Zhang, Y. Ding, W. Fan, L. Sun, X.
Zhao, H. Lei, Cryst. Growth Des. 2013, 13, 2462–2475.
Chem. Eur. J. 2013, 00, 0 – 0
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www.chemeurj.org
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S. S. Lee, K.-M. Park et al.
[8] X. Bao, J.-L. Liu, J.-D. Leng, Z. Lin, M.-L. Tong, M. Nihei, H.
Oshio, Chem. Eur. J. 2010, 16, 6169.
[12] a) K.-M. Park, J. Seo, S.-H. Moon, S. S. Lee, Cryst. Growth Des.
2010, 10, 4148–4154; b) C. Barkenbus, E. B. Friedman, R. K. Flege,
J. Am. Chem. Soc. 1927, 49, 2549–2553; c) Y. W. Park, Y. Na, D.-J.
Baek, Bull. Korean Chem. Soc. 2006, 27, 2023–2027.
[13] H. S. Harned, B. B. Owen, The Physical Chemistry of Electrolyte
Solutions, Reinhold, New York, USA 1958.
[14] APEX2 Version 2009.1-0 Data collection and Processing Software,
Bruker AXS Inc., Madison, Wisconsin, USA 2008.
[15] SHELXTL-PC Version 6.22: Program for Solution and Refinement
of Crystal Structures, Bruker AXS Inc., Madison, Wisconsin, USA
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[9] Z.-M. Hao, X.-M. Zhang, Cryst. Growth Des. 2007, 7, 64–68.
[10] a) S. Park, S. Y. Lee, K.-M. Park, S. S. Lee, Acc. Chem. Res. 2012,
45, 391–403; b) H. J. Kim, L. F. Lindoy, S. S. Lee, Cryst. Growth
Des. 2010, 10, 3850–3853; c) S. Park, S. Y. Lee, M. Jo, J. Y. Lee, S. S.
Lee, CrystEngComm 2009, 11, 43–46; d) J. Seo, M. R. Song, J.-E.
Lee, S. Y. Lee, I. Yoon, K.-M. Park, J. Kim, J. H. Jung, S. B. Park,
S. S. Lee, Inorg. Chem. 2006, 45, 952–954; e) S. Y. Lee, J. Seo, I.
Yoon, C.-S. Kim, K. S. Choi, J. S. Kim, S. S. Lee, Eur. J. Inorg.
Chem. 2006, 3525–3531.
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Li, Z.-Y. Li, CrystEngComm 2008, 10, 590–597.
Received: July 7, 2013
Published online: && &&, 0000
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Supramolecular Isomerism
COMMUNICATION
Supramolecular Chemistry
E. Lee, J.-Y. Kim, S. S. Lee,*
K.-M. Park* ................... &&&& — &&&&
Molar-Ratio-Dependent Supramolec-
ular Isomerism: AgI Coordination
Polymers with Bis(cyanobenzyl)sul-
fides
The ratio is the key: On varying the
molar ratio of the reactants, AgNO3
and tridentate m-L ligand, supramolec-
ular isomers 1 and 2 comprising a 2D
polymeric network were obtained.
Conformational differences of m-L
play a crucial role in the 2D network
structures adopted for isomers 1 and 2.
Supramolecular Isomerism
Silver supramolecular isomers 1 and 2 each comprising a
2D polymeric coordination network were obtained on
varying the molar ratio of the reactants (silver and a
ligand based on bis(cyanobenzyl)sulfide). Notably, the
overall structural motifs of 1 and 2 are mainly due to the
conformational variation of the ligand: “S”-shaped in 1
and “V”-shaped in 2. More details of this interesting
supramolecular isomerism are given by S. S. Lee, K.-M.
Park et al. in their Communication on page && ff.
Chem. Eur. J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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These are not the final page numbers!