Silver(I) and copper(I) coordination polymers based on thiaoxa-macrocycles

Article abstract of DOI:10.1002/ejic.200800284

Two S₂O₂-macrocycles with different ring size (L ¹: 17- and L²: 18-membered) were synthesised and structurally characterised by X-ray analysis. Reactions of L¹ and L² with silver(I) salts (

Full text of DOI:10.1002/ejic.200800284

FULL PAPER
DOI: 10.1002/ejic.200800284
Silver(I) and Copper(I) Coordination Polymers Based on Thiaoxa-Macrocycles
Hyun Jee Kim,[a] Mi Ryoung Song,[a] So Young Lee,[a] Jai Young Lee,[a] and
Shim Sung Lee*[a]
Keywords: Macrocycles / Silver / Copper / Coordination polymers
Two S2O2-macrocycles with different ring size (L1: 17- and
L2: 18-membered) were synthesised and structurally charac-
terised by X-ray analysis. Reactions of L1 and L2 with silver(I)
while, reactions of these two ligands with copper(I) iodide
afforded 1D (5) and 2D (6a) coordination polymers linked
with a rhomboid-type Cu–I2–Cu unit, respectively. The for-
mation of such discrete and continuous supramolecular com-
plexes is discussed in terms of discrimination of the anion
effect, ligand flexibility as well as interligand π-π stacking
interaction.
–
salts (ClO4 and NO3–) afforded respective ligand- and/or
anion-directed complexes 1–4 with different topologies; sin-
gle-stranded 1D coordination polymer [AgL1(ClO4)(DMSO)]n
(1), double-stranded 1D coordination polymer {[Ag2(L1)2-
(NO3)2]·DMSO}n (2), cyclic dimer [Ag2(L2)2(ClO4)2]·CH2Cl2·
CH3OH (3) and 2D polymeric sheet [Ag(L2)NO3]n (4). Mean-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
differences in supramolecular level (assembled product)”.
For example, in view of both the silver(I) salts and cop-
per(I) iodide system employed, it is becoming apparent that
such a small variation of ligand structure plays an impor-
tant role in the topologies of resulting complexes.
Introduction
The sulfur-bearing crown ethers (thiamacrocycles) show
remarkable coordinating ability to form stable complexes
with d-block metal ions, in many cases forcing the metal
ion to adopt an unusual position.[1] Our group[2] and
others[3] have proposed the exo-coordination behaviour of
the thiamacrocycles, which exhibit diverse types of supra-
molecular complexes with soft metal salts upon varying do-
nor atoms and anions. Recently, we reported that simple
tuning of interdonor (S···S) separation in given S2O2-
macrocycles as a controlling factor is effective to discrimi-
nate the products because of the different exo-binding mode
towards the soft metal ions.[4] Parallel to this, coordination
of copper(I) halide with the same ligand system is of par-
ticular interest due to the diverse binding mode of copper(I)
halide clusters towards the ligand and their unique photo-
physical properties.[5] On the basis of these considerations,
we are interested in extending this approach to the nonco-
ordinating donors of similar ligand systems. Taking these
into account, two analogous S2O2 macrocycles L1 (17-mem-
bered) and L2 (18-membered) with variation of flexibility
due to the slightly different ring sizes are synthesised. We
reasoned that these may trigger discrimination of rigidity-
controlled products with soft metal ions, such as silver(I)
and copper(I). As a result, we have realised that “small
changes in molecular level (building block) can induce large
Results and Discussion
Synthesis and Characterisation of Ligands
Synthesis of the ligands began with salicylaldehyde
(Scheme 1). Dichloride precursors[6] for cyclisation were
prepared through macrocyclisation reactions from corre-
sponding dichlorides and 1,3-phenylenedimethanethiol in
the presence of Cs2CO3 under high dilution conditions in
reasonable yields (L1: 30% and L2: 50%).
[a] Department of Chemistry (BK21) and Research Institute of
Natural Science, Gyeongsang National University,
Jinju 660-701, Korea
Scheme 1. Synthesis of ligands L1 and L2.
Fax: +82-55-753-7614
E-mail: sslee@gnu.ac.kr
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Structures of the macrocycles prepared were also charac-
terised in solid-state by single-crystal X-ray crystallography
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Silver(I) and Copper(I) Coordination Polymers
(Figure 1). Colourless crystals of L1 and L2 suitable for X- Syntheses of Silver(I) Complexes and Structural Description
ray analysis were obtained by slow evaporation from the
In complexation with silver(I), perchlorate and nitrate
were used to examine the anion effect on resulting com-
plexes. Using these reaction systems, we obtained four
supramolecular complexes 1–4 with different topologies
(Scheme 2), and their structures were characterised by X-
ray analysis (Figures 2, 3, 4 and 6).
respective solutions of dichloromethane. Without excep-
tion, O atoms are oriented in an endodentate fashion, while
S atoms are positioned exodentate.[7] The macrocyclic ring
of L1 is slightly twisted and the torsion angle between two
O atoms is indicative of a gauche arrangement [O1–C–C–
O2 67.2(3)°]. L2 shows a more twisted configuration due to
the flexible nature of the ring cavity than that of L1. Thus,
the O···O distance in L2 [4.115(3) Å] is longer than that of
L1 [2.870(2) Å], but the S···S distance in L2 [6.436(1) Å] is
shorter than that in L1 [7.156(1) Å], indicating the flexible
nature of L2.
Figure 1. Molecular structures of (a) L1, and (b) L2.
Scheme 2. Silver(I) complexes prepared.
Figure 2. Single-stranded 1D polymeric structure of 1, [Ag(L1)(ClO4)(DMSO)]n. Hydrogen atoms are omitted for clarity. Selected bond
lengths [Å] and angles [°]: Ag1–O7 2.347(3), Ag1–O3 2.448(4), Ag1–S1A 2.478(1), Ag1–S2 2.487(1), O7–Ag1–O3 115.5(1), O7–Ag1–S1A
103.0(1), O3–Ag1–S1A 96.8(1), O7–Ag1–S2 99.9(1), O3–Ag1–S2 113.0(1), S1A–Ag1–S2 129.3(4). Symmetry operation: A: x, y + 1, z.
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the continual symmetry operations. The Ag1 atom which
links two macrocycles via Ag–S bonds shows distorted tet-
rahedral coordination composed of two S donor atoms
–
from two L1, one monodentate ClO4 and one DMSO
molecule. Two O donor atoms in the ring cavity remain un-
coordinated. The largest deviations from tetrahedral coor-
dination around Ag involve the angles O6–Ag–S1A
[96.8(1)°] and S2–Ag1–S1A [129.3(4)°]. The conformation
of L1 in 1 is not significantly different from that in free L1,
suggesting that the ligand is relatively well preorganised. It
is also noteworthy that the coordinated macrocycles are ar-
ranged side by side showing the interligand π-π stacking
(dashed lines in Figure S1; see Supporting Information) be-
tween two benzo-groups in adjacent ligands. The preference
for the 1D array, in this case, is probably due to the interli-
gand π-π stacking observed for all of the L1 complexes in
this work (see below).
Figure 3. Double-stranded 1D polymeric structure of 2, {[Ag2(L1)2-
(NO3)2]·DMSO}n. Hydrogen atoms and noncoordinating solvent
molecules are omitted for clarity. Selected bond lengths [Å] and
angles [°]: Ag1–O3 2.454(2), Ag1–S2 2.463(1), Ag1–S1A 2.476(1),
Ag1–O5 2.501(4), O3–Ag1–S2 105.8(1), O3–Ag1–S1A 108.0(1),
S2–Ag1–S1A 132.1(4), O3–Ag1–O5 82.3(1), S2–Ag1–O5 119.0(1),
S1A–Ag1–O5 98.7(1). Symmetry operation: A: x, y, z – 1.
To examine the role of anions in the formation of L1
complexes, the reaction was repeated with AgNO3. Reac-
tion of L1 and AgNO3 in CH2Cl2/CH3OH afforded a pre-
cipitate immediately. The precipitate was filtered and col-
lected. The colourless crystalline product 2 was grown by
vapour diffusion of diethyl ether into DMF/DMSO solu-
tion of the complex. The structure of 2 is more interesting.
The X-ray analysis revealed that 2 is a double-stranded 1D
array of formula {[Ag2(L1)2(NO3)2]·DMSO}n (Figure 3).
The asymmetric unit contains one L1, one Ag atom, a half
of a monodentate nitrate ion and a half of a bidentate ni-
trate ion. Each Ag atom outside the cavity is four-coordi-
nate by two S atoms from two adjacent L1 forming an Ag–
L1–Ag–L1 array. The remaining sites are occupied by one
mono- and one bidentate nitrate ion which bridge two ar-
rays via Ag–O(NO)O–Ag and Ag–O(NO2)–Ag bonds. In
other words, the Ag–(NO3)2–Ag bridging units are located
at the centre of four L1 and each Ag atom is tetrahedrally
coordinated by two S donors from two adjacent L1 by Ag–
S bonds and two O atoms from two bridging nitrate ions
forming an infinite poly(cyclic dimer) structure. Unlike the
case of 1, one DMSO molecule was found uncoordinated
in the cavity. The S2–Ag–S1A angle for the different macro-
cycles is 132.1(4)° and the S2–Ag–O3 and S1A–Ag–O5
angles are 105.8(1) and 98.7(1)°, respectively. Some discrete
and polymeric species linked with the square-dimer Ag–
(NO3)2–Ag unit have been reported.[8] To the best of our
knowledge, this is the first characterised example of a dis-
ilver system doubly bridged by one mono- and one biden-
tate nitrate ion. The interligand π-π stacking (dashed lines
Figure 4. Cyclic dimer structure of 3, [Ag2(L2)2(ClO4)2]·
CH2Cl2·CH3OH. Hydrogen atoms and noncoordinating solvent
molecules are omitted for clarity. Selected bond lengths [Å] and
angles [°]: Ag1–S1A 2.420(1), Ag1–S2 2.426(1), Ag1–O3 2.636(3),
S1A–Ag1–S2 161.8(1), S1–Ag1–O3 86.2(1), S1A–Ag1–O3 107.0(1).
Symmetry operation: A: –x + 1, –y + 1, –z + 1.
–
From the reactions of L1 with silver(I) salts (1: ClO4
–
and 2: NO3 ), two complexes 1 and 2 were prepared as fol- in Figure S2) between two benzo groups in adjacent ligands
lows. Each colourless precipitate was obtained from L1 with is also observed. As a result, the nitrate ions as the second
the corresponding silver(I) salts in CH2Cl2/CH3OH and sin- coordinating species and interligand π-π stacking both
gle crystals of the respective complexes suitable for X-ray show an influence on the assembled structure of 2.
analysis were obtained by vapour diffusion of diethyl ether
Having successfully obtained L1 complexes (1 and 2), we
into the DMSO solution. The X-ray analysis revealed that proceeded with the preparation of L2 complexes (3 and 4).
1 is a unique single-stranded 1D polymeric array of formula Colourless crystalline complex 3 was obtained by slow con-
[AgL1(ClO4)(DMSO)]n with a –L1–Ag–L1–Ag pattern (Fig- centration of the reaction mixture of L2 and AgClO4 in
ure 2). Thus, the asymmetric unit of 1 contains one L1, one CH2Cl2/CH3OH at room temperature. The X-ray analysis
Ag atom, one perchlorate ion and one DMSO molecule. revealed that 3 is a discrete-type cyclic dimer of formula
The structural unit shown in Figure 2 is generated through [Ag2(L2)2(ClO4)2]·CH2Cl2·CH3OH (Figure 4). The asym-
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Silver(I) and Copper(I) Coordination Polymers
metric unit contains one L2, one Ag atom, one perchlorate
ion and two noncoordinating solvent molecules (not
shown). The structural unit shown in Figure 4 is generated
through an inversion symmetry. Each three-coordinate Ag
atom that lies outside the cavity bridges two S donors from
two facing macrocycles. The coordination geometry of the
Ag atom is trigonal planar with two coordination sites be-
ing occupied by the S atoms and the third site occupied by
a monodentate perchlorate ion. The trigonal planar silver(I)
is considerably distorted from the regular one to give a T-
shaped geometry: the bond angles for S2–Ag1–S1A, S2–
Ag1–O3 and S1A–Ag1–O3 are 161.8(1)°, 86.2(1)° and
107.0(1)°, respectively. The difference in the bond angles
around the Ag centre is caused by the steric hindrance of
the macrocycles.
Figure 5. Observed isotopic distribution for [Ag2(L2)2(ClO4)]+ in
the FAB mass spectrum of 3. The bars represent the predicted mass
spectral distribution for this ion.
The FAB mass spectrum of 3 contains a peak at m/z an Ag–(µ-NO3)2–Ag rhomboid core bonded to four ligands
1159, which corresponds to [Ag2(L2)2(ClO4)]+, according to via Ag–S bonds (Figure 6, a). The Ag atom is tetrahedrally
its isotope pattern (Figure 5).
coordinated by two S donors from two adjacent ligands and
Colourless crystalline complex 4 was obtained by slow two monodentate µ2-NO3 ions. The Ag–S [2.416(1) and
concentration of a reaction mixture of L2 and AgNO3 in 2.514(1) Å] and Ag–O [2.391(2) and 2.444(2) Å] bond
CH2Cl2/CH3OH at room temperature. The X-ray analysis lengths are reasonably similar to those in other complexes.[9]
revealed that 4 is a 2D polymeric array of formula [AgL(µ- The gross geometry of 4 can be described as an infinite
NO3)]n (Figure 6). The 2D network of 4 basically contains brick-wall pattern (Figure 6, b). The asymmetric unit of 4
Figure 6. (a) Coordination environment of 4, [Ag(L2)NO3]n, (b) brick-wall type 2D polymeric network, (c) a single brick unit in 4
generated through four L2 and four Ag–(µ-NO3)2–Ag rhomboid cores and (d) side view of wavy 2D network. Selected bond lengths [Å]
and angles [°]: Ag1–O3 2.391(2), Ag1–S1 2.416(1), Ag1–O3A 2.444(2), Ag1–S2B 2.514(1), O3–Ag1–S1 117.3(1), O3–Ag1–O3A 71.1(1),
S1–Ag1–O3A 134.3(1), O3–Ag1–S2B 100.1(1), S1–Ag1–S2B 127.3(2), O3A–Ag1–S2B 91.0(1). Symmetry operations: A: –x + 2, –y + 2,
–z + 1, B: –x + 3/2, y + 1/2, –z + 3/2.
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contains one L2, one Ag atom and one nitrate ion. A single 2D polymeric scaffold is probably due to the flexible nature
brick unit of 4 contains four asymmetric units where each of L2 together with the steric effect (hindrance) between the
ligand is interconnected by the Ag–(µ-NO3)2–Ag linkers macrocycles.
alternately (Figure 6, c). In this case, the preference for the
Syntheses of Copper(I) Iodide Complexes and Structural
Description
As mentioned, the ligand-directed products 5 and 6a
with different topologies were obtained by the assembly re-
actions of each ligand with copper(I) iodide as depicted in
Scheme 3.
Figure 7. Double-stranded 1D polymeric structure of 5,
[(Cu2I2)(L1)2]n. Selected bond lengths [Å] and angles [°]: Cu1–S1A
2.332(2), Cu1–S2 2.371(2), Cu1–I1 2.617(1), Cu1–I1B 2.677(1),
S1A–Cu1–S2 112.1(1), S1A–Cu1–I1 109.8(1), S2–Cu1–I1 112.7(1),
S1A–Cu1–I1B 103.5(1), S2–Cu1–I1B 109.3(1), I1–Cu1–I1B
109.1(1), Cu1–I1–Cu1B 70.9(1). Symmetry operations: A: x, y + 1,
Scheme 3. Copper(I) iodide coordination polymers prepared.
z, B: –x + 1, –y + 2, –z + 1.
Figure 8. (a) Coordination environment of 6a, [(Cu2I2)(L2)2]n, (b) brick-wall-type 2D polymeric network, (c) a single brick unit in 6a
generated through four L2 and four Cu–I2–Cu rhomboid cores. Selected bond lengths [Å] and angles [°]: Cu1–S2A 2.307(1), Cu1–S1
2.352(1), Cu1–I1 2.646(1), Cu1–I1B 2.674(1), I1–Cu1B 2.674(1), S2A–Cu1–S1 111.1(4), S2A–Cu1–I1 108.5(3), S1–Cu1–I1 104.7(3), S2A–
Cu1–I1B 118.8(3), S1–Cu1–I1B 105.9(3), I1–Cu1–I1B 106.9(2), Cu1–I1–Cu1B 73.1(2). Symmetry operations: A: –x + 1/2, y + 1/2, – z +
1/2, B: –x, –y + 2, –z + 1.
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Silver(I) and Copper(I) Coordination Polymers
Slow diffusion of dichloromethane solution of L1 into an bility due to the different ring sizes were synthesised and
acetonitrile solution of CuI afforded pale yellow crystalline structurally characterised. Five coordination polymers and
product 5. Complex 5 features a double-stranded 1D poly- one metallo-cyclic dimer were obtained from the assembly
mer with formula [(Cu2I2)(L1)2]n (Figure 7). Each L1 is reactions of the macrocycles with the silver salts (perchlo-
linked with the Cu–I2–Cu rhomboid unit via Cu–S bonds. rate and nitrate) and copper(I) iodide. The versatility of re-
The copper(I) coordination sphere is a distorted tetrahedral sults has been discussed with emphasis placed on the influ-
shape, with the tetrahedral angles falling in the range ences of the ring flexibility of the macrocycles, variation of
103.5(1)–112.7(1)°. Only two examples of thia-macrocycles anions and interligand π-π stacking of the respective supra-
yielding coordination polymers incorporating a double- molecular complexes.
stranded 1D copper(I) halide coordination polymer are re-
ported.[10]
The reaction of L2 with CuI afforded a mixed product
(6a and 6b) with a pale-yellow colour which can be sepa-
rated manually into two pure species under an optical
microscope; block crystals of 6a and powdered 6b were thus
obtained. The X-ray analysis revealed that 6a is a 2D poly-
meric array of formula [(Cu2I2)(L2)2]n (Figure 8). The 2D
network of 6a contains a Cu–I2–Cu rhomboid core bonded
to four ligands via Cu–S bonds (Figure 8, a). So, the infinite
brick-wall-type gross geometry of 6a is similar to that of 4
(Figure 6, b and Figure 8, b). The asymmetric unit of 6a
contains one L2, one Cu atom and one I atom. A single
brick unit of 6a contains four asymmetric units where each
ligand is interconnected by the Cu–I2–Cu linking units
alternately but no solvent molecule is included inside (Fig-
ure 8, c). Consequently, the flexible nature of L2 together
with the steric effect (hindrance) between the macrocycles
may, in part, produce the sheet-type polymeric scaffold.
Some other examples of layered copper(I) halide complexes
with thiamacrocycles have been reported by our group[11]
and others.[12] Figure 9 shows the emission spectra of 6a
and 6b at room temperature in the solid state. In contrast
to 6a, 6b exhibits a broad band with bright-yellow emission
maxima at 570 nm arising from the cluster-centred excited
state with mixed halide-to-metal charge transfer charac-
ter.[5]
Experimental Section
General Remarks: Chemical reagents and solvents were purchased
commercially and used as received without further purification. In-
frared spectra were measured with a Mattson Genesis Series FT-
IR spectrophotometer, and the NMR spectra were recorded with
a Bruker 300 MHz spectrometer. Mass spectra were obtained with
an Applied Biosystems QTRAP-3200 (ESI) or JEOL JMS-700
(FAB) spectrometer at the Central Laboratory of Gyeongsang
National University.
Synthesis and Characterisation of L1: Cs2CO3 (9.78 g, 30.0 mmol)
was dissolved in DMF (1 L) in a flask; also a syringe was filled
with 2,2Ј-(ethylenedioxy)bis(benzyl chloride) (4.65 g, 15.0 mmol)
and 1,3-phenylenedimethanethiol (2.55 g, 15.0 mmol) dissolved in
DMF (30 mL). Under a nitrogen atmosphere, the content of the
syringe was added at regular speed (0.6 mL/h) into the DMF solu-
tion maintaining 45–50 °C. After cooling to room temperature the
reaction mixture was filtered and the solvent was removed. Water
(100 mL) was added, and the mixture was extracted with CH2Cl2.
Flash column chromatography on silica gel using dichloromethane/
n-hexane gave L1 as a white solid. Yield 1.97 g (30%); m.p. 137–
139 °C (decomp.). C24H24O2S2 (408.58): calcd. C 70.55, H 5.92, S
15.70; found C 70.40, H 6.02, S 15.68. IR (KBr): ν = 2935, 2363,
˜
2330, 1588, 1487, 1447, 1102, 1064, 940, 715 cm–1. 1H NMR
(300 MHz, CDCl3): δ = 6.74–7.50 (m, 12 H, Ar), 4.19 (s, 4 H,
OCH2), 3.68 (s, 4 H, OArCH2S), 3.66 (s, 4 H, ArCH2S) ppm. 13C
NMR (75 MHz, CDCl3): δ = 158.5, 156.0, 137.3, 130.5, 128.1,
126.6, 121.1, 121.0, 111.5, 66.2, 38.0, 29.7 ppm. MS: m/z 408
[C24H24O2S2]+.
Synthesis and Characterisation of L2: Synthetic procedure was al-
most the same as for L1 except for the use of 2,2Ј-(propylenedioxy)-
bis(benzyl chloride). The flash column chromatography (SiO2;
dichloromethane/n-hexane, 1:3) afforded the product as a white so-
lid in 50% yield; m.p. 120–123 °C (decomp.). C25H26O2S2 (422.60):
calcd. C 71.05, H 6.20, S 15.18; found C 71.17, H 6.24, S 15.11.
IR (KBr): ν = 3070, 3033, 2916, 2865, 2361, 2339, 1587, 1500, 1448,
˜
1237, 1098, 1025, 755, 711, 670 cm–1. 1H NMR (300 MHz, CDCl3):
δ = 6.81–7.31 (m, 12 H, Ar), 4.15 (t, 4 H, OCH2), 3.73 (s, 4 H,
OArCH2S), 3.64 (s, 4 H, ArCH2S), 2.15 (m, 2 H, OCH2CH2) ppm.
13C NMR (75 MHz, CDCl3): δ = 156.5, 139.0, 130.8, 128.7, 128.3,
127.0, 126.9, 120.7, 112.0, 64.6, 36.0, 30.7, 28.4 ppm. MS: m/z 423.2
[C25H26O2S2]+.
[Ag(L1)(ClO4)(DMSO)]n (1): AgClO4 (15.0 mg, 0.074 mmol) was
dissolved in methanol (2 mL) and added to a solution of L1
(30.0 mg, 0.074 mmol) in dichloromethane. The white precipitate
(41.0 mg, 0.067 mmol) in 92% yield formed immediately. The pre-
cipitate was filtered off, washed with methanol and diethyl ether
and dried in vacuo. Single crystals suitable for X-ray analysis were
obtained by vapour diffusion with diethyl ether into DMSO solu-
tion (2 mL); m.p. 198–200 °C (decomp.). C26H30AgClO7S3
Figure 9. Solid-state emission spectra of 6a (dashed line) and 6b
(solid line) at room temperature excited at 360 nm.
Conclusions
In summary, two analogous dithiamacrocycles L1 (17-
membered) and L2 (18-membered) with variation of flexi- (694.03): calcd. C 45.00, H 4.36, S 13.86; found C 45.20, H 4.41, S
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FULL PAPER
14.00. IR (KBr): ν = 2937, 1595, 1487, 1448, 1244, 1229, 1148,
750, 711, 620 cm–1. MS: m/z 1159.07 [C25H26O2S2]+. MS: m/z 1159
[Ag2(L2)2(ClO4)]+.
˜
1113, 1103, 1080, 1065, 941, 752, 710, 625 cm–1.
[Ag(L2)NO3]n (4): AgNO3 (7.01 mg, 0.041 mmol) was dissolved in
methanol (2 mL) and added to a solution of L2 (15.0 mg,
0.035 mmol) in dichloromethane. Single crystals suitable for X-ray
analysis were obtained by slow concentration. Yield ca. 50%; m.p.
160–165 °C (decomp.). C25H26AgNO5S2 (592.48): calcd. C 50.68,
H 4.42, N 2.36, S 10.82; found C 50.83, H 4.37, N 2.57, S 10.74.
{[Ag2(L1)2(NO3)2]·DMSO}n (2): AgNO3 (13.0 mg, 0.074 mmol)
was dissolved in methanol (2 mL) and added to a solution of L1
(30.0 mg, 0.074 mmol) in dichloromethane. A white precipitate
(39.0 mg, 0.067 mmol) was formed immediately, 90% yield. The
precipitate was filtered off, washed with methanol and diethyl ether
and dried in vacuo. Single crystals suitable for X-ray analysis were
obtained by vapour diffusion with diethyl ether into DMSO
and DMF solution (2 mL); m.p. 196–198 °C (decomp.).
C50H54Ag2N2O11S5 (1235.03): calcd. C 48.63, H 4.41, N 2.27, S
IR (KBr): ν = 3067, 3024, 2955, 2933, 2882, 2867, 2360, 2340, 1652,
˜
1635, 1554, 1543, 1492, 1454, 1425, 1384, 1281, 1241, 1102, 1019,
760, 717, 668 cm–1.
[(Cu2I2)(L1)2]n (5): A dichloromethane (2 mL) solution of L1
(30.1 mg, 0.074 mmol) was allowed to diffuse slowly to an acetoni-
trile (2 mL) solution of CuI (14.0 mg, 0.074 mmol) in a capillary
tube (i.d. 5 mm). The pale yellow single crystals suitable for X-ray
analysis were obtained in the tube. Yield ca. 50%; m.p. 197–198 °C
(decomp.). C24H24CuIO2S2 (599.03): calcd. C 48.12, H 4.04, S
12.98; found C 48.48, H 4.52, N 2.30, S 13.01. IR (KBr): ν = 2941,
˜
2343, 1591, 1491, 1439, 1410, 1385, 1362, 1317, 1292, 1252, 1225,
1188, 1103, 1045, 931, 754, 714 cm–1.
[Ag2(L2)2(ClO4)2]·CH2Cl2·CH3OH
(3):
AgClO4
(8.01 mg,
0.038 mmol) was dissolved in methanol (2 mL) and added to a
solution of L2 (15.0 mg, 0.035 mmol) in dichloromethane. Single
crystals suitable for X-ray analysis were obtained by slow con-
centration. Yield ca. 50%; m.p. 180–184 °C (decomp.).
C25H26AgClO6S2 (629.92): calcd. C 47.67, H 4.16, S 10.18; found
10.71; found C 48.36, H 4.11, S 10.82. IR (KBr): ν = 2923, 1587,
˜
1491, 1454, 1292, 1250, 1222, 1103, 1053, 937, 750, 710 cm–1.
[(Cu2I2)(L2)2]n (6a) and [(Cu4I4)(L2)2]n (6b): A dichloromethane
(2 mL) solution of L2 (15.0 mg, 0.035 mmol) was allowed to diffuse
slowly to an acetonitrile (2 mL) solution of CuI (8.01 mg,
C 47.53, H 4.19, S 10.20. IR (KBr): ν = 3064, 3041, 2955, 2932,
˜
2878, 2360, 2343, 1596, 1585, 1491, 1455, 1243, 1101, 1056, 953,
Table 1. Relevant crystal data collection and refinement data for the crystal structures of L1, L2, and 1–6a.
L1
L2
1
2
Empirical formula
Formula mass
Temperature [K]
Crystal system
Space group
Z
a [Å]
b [Å]
c [Å]
α [°]
C24H24O2S2
408.55
173(2)
monoclinic
P21/c
4
8.7931(5)
23.8008(14)
10.2176(6)
90
106.4270(10)
90
2051.1(2)
1.323
54.00
C25H26O2S2
422.58
173(2)
triclinic
P-1
C26H30AgClO7S3
694.00
173(2)
triclinic
P-1
C50H54Ag2N2O11S5
1234.99
173(2)
monoclinic
P21/m
2
8.4446(4)
27.3965(14)
11.2232(6)
90
98.8290(10)
90
2565.7(2)
1.599
55.00
2
2
8.1852(8)
10.1526(9)
13.3760(12)
93.562(2)
90.205(2)
96.644(2)
1101.90(18)
1.274
8.5370(8)
11.2691(10)
15.0738(14)
94.712(2)
94.964(2)
100.500(2)
1413.4(2)
1.072
β [°]
γ [°]
V [Å3]
Dx [gcm–3]
2θmax [°]
R
52.00
0.0456
53.00
0.0410
0.0558
0.0487
wR
0.1148
4448 [R(int) = 0.0470]
0.1043
4250 [R(int) = 0.0517]
0.0898
5746 [R(int) = 0.0279]
0.0893
5849 [R(int) = 0.0469]
No. of reflections
used [I Ͼ 2σ(I)]
3
4
5
6
Empirical formula
Formula mass
Temperature [K]
Crystal system
Space group
Z
a [Å]
b [Å]
c [Å]
α [°]
C52H57.6Ag2Cl4.4O12.8S4
1387.34
173(2)
monoclinic
P21/c
2
14.0598(8)
9.6617(5)
22.2090(12)
90
104.5720(10)
90
2919.9(3)
1.578
54.00
C25H26AgNO5S2
592.46
173(2)
monoclinic
P21/n
4
10.6473(4)
17.7381(6)
13.0668(4)
90
90.2700(10)
90
2467.81(15)
1.595
54.00
C49H50Cl2Cu2I2O4S4
1282.91
173(2)
C25H26CuIO2S2
613.02
173(2)
monoclinic
P21/n
4
11.4183(5)
17.1126(7)
12.1539(5)
90
91.0480(10)
90
2374.38(17)
1.715
53.98
triclinic
¯
P1
1
8.4742(9)
11.0406(11)
13.8713(14)
105.921(2)
92.628(2)
100.479(2)
1220.9(2)
1.745
β [°]
γ [°]
V [Å3]
Dx [gcm–3]
2θmax [°]
R
52.00
0.0507
0.0436
0.0305
0.0301
wR
0.1156
6353 [R(int) = 0.0259]
0.0747
5387 [R(int) = 0.0230]
0.1268
4683 [R(int) = 0.0193]
0.0651
5140 [R(int) = 0.0304]
No. of reflections
used [I Ͼ 2σ(I)]
3538
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 3532–3539

Silver(I) and Copper(I) Coordination Polymers
[3]
a) S. Wolfe, Acc. Chem. Res. 1972, 5, 102–111; b) G. H. Robin-
son, S. A. Sangokova, J. Am. Chem. Soc. 1988, 110, 1494–1497;
c) J. Buter, R. M. Kellog, F. van Bolhuis, J. Chem. Soc., Chem.
Commun. 1991, 910–912; d) S. E. Hill, D. Feller, J. Phys. Chem.
A 2000, 104, 652–660.
S. Y. Lee, S. Park, H. J. Kim, J. H. Jung, S. S. Lee, Inorg. Chem.
2008, 47, 1913–1915.
a) M. R. Churchill, F. J. Rotella, Inorg. Chem. 1977, 16, 3267–
3273; b) O. A. Babich, V. N. Kokozay, Polyhedron 1997, 16,
1487–1490; c) P. R. Ashton, A. L. Burns, C. G. Claessens,
G. K. H. Shimizu, K. Small, J. F. Stoddart, A. J. P. White, D. J.
Williams, J. Chem. Soc., Dalton Trans. 1997, 1493–1496; d)
P. M. Graham, R. D. Pike, Inorg. Chem. 2000, 39, 5121–5132;
e) M. Vitale, W. E. Palke, P. C. Ford, J. Phys. Chem. 1992, 96,
8329–8336; f) T. H. Kim, K. Y. Lee, Y. W. Shin, S.-T. Moon,
K.-M. Park, J. S. Kim, Y. Kang, S. S. Lee, J. Kim, Inorg. Chem.
Commun. 2005, 8, 27–30.
a) I. M. Atkinson, L. F. Lindoy, O. A. Matthews, G. V. Mee-
han, A. N. Sobolev, A. H. White, Aust. J. Chem. 1994, 47,
1155–1162; b) Y. A. Ibrahim, A. H. M. Elwahy, G. M. M. Elk-
areish, J. Chem. Res. Synop. 1994, 11, 414.
R. E. Wolf Jr, J. R. Hartman, J. M. E. Storey, B. M. Foxman,
S. R. Cooper, J. Am. Chem. Soc. 1987, 109, 4328–4335.
a) D. Fortin, M. Drouin, P. D. Herring, D. A. Summers, R. C.
Thompson, Inorg. Chem. 1999, 38, 1253–1260; b) M. Ahlgren,
T. Pakkanen, I. Rahvanainen, Acta Chem. Scand. A 1985, 39,
651; c) F. Bachechi, A. Curini, R. Galassi, A. Macchioni, B. R.
Pietroni, F. Ziarelli, C. Zuccaccia, J. Organomet. Chem. 2000,
593, 392–420; d) J. T. Sampanthar, J. J. Vittal, Cryst. Eng. 2000,
3, 117–133; e) J. H. Meiners, J. C. Clardy, J. G. Verkade, Inorg.
Chem. 1975, 14, 632–636; f) F. Caruso, M. Camalli, H. Rimml,
L. M. Venanzi, Inorg. Chem. 1995, 34, 673–679.
a) P. G. Jones, T. Gries, H. Grutzmacher, H. W. Roesky, J.
Schimkowiak, G. M. Sheldrick, Angew. Chem. Int. Ed. Engl.
1984, 23, 376; b) Q.-M. Wang, T. C. W. Mak, Chem. Eur. J.
2003, 9, 43–50; c) A. J. Blake, N. R. Champness, S. M. Howdle,
K. S. Morley, P. B. Webb, C. Wilson, Cryst. Eng. Commun.
2002, 4, 88–92; d) M. Fainerman-Melnikova, L. F. Lindoy, S.-
Y. Liou, J. C. McMurtrie, N. P. Green, A. Nezhadali, G. Roun-
aghi, W. N. Setzer, Aust. J. Chem. 2004, 57, 161–166; e) A. J.
Blake, W.-S. Li, V. Lippolis, M. Schröder, Chem. Commun.
1997, 1943–1944.
0.042 mmol) in a capillary tube (i.d. 5 mm). A mixture of the pale-
yellow X-ray-quality crystals (6a) and pale-yellow powder (6b) were
obtained in the tube. The mixture was separated into two pure
species manually under an optical microscope. 6a: Yield ca. 20%;
m.p. 225–228 °C (decomp.). C25H26CuIO2S2 (613.05): calcd. C
44.88, H 4.27, S 10.46; found C 44.79, H 4.37, S 10.49. IR (KBr):
[4]
[5]
ν = 3064, 3040, 2951, 2912, 2873, 1597, 1586, 1494, 1452, 1241,
˜
1099, 1062, 1028, 960, 757, 717, 666 cm–1. 6b: Yield ca. 40%; m.p.
270–272 °C (decomp.). C25H26Cu2I2O2S2: calcd. C 37.37, H 3.26,
S 7.98; found C 37.55, H 3.29, S 7.97. IR (KBr): ν = 3056, 3037,
˜
2956, 2914, 2867, 2349, 1597, 1585, 1493, 1452, 1244, 1101, 1060,
1022, 958, 748, 719, 700 cm–1.
CAUTION! Perchlorate salts of metal complexes are potentially
explosive and should be handled with great care.
X-ray Crystallography: All data were collected with a Bruker Smart
diffractometer equipped with a graphite-monochromated Mo-Kα (λ
= 0.71073 Å) radiation source and a CCD detector. The 45 frames
of two-dimensional diffraction images were collected and processed
to obtain the cell parameters and orientation matrix. The first 50
frames were retaken after complete data collection. The crystal
showed no significant decay. The frame data were processed to give
structure factors using the SAINT program.[13] The structure was
solved by direct methods and refined by full-matrix least-squares
methods on F2 for all data using SHELXTL software.[14] The non-
hydrogen atoms were refined anisotropically. Relevant crystal data
collection and refinement data for the crystal structures of L1, L2,
and 1–6a are summarised in Table 1.
[6]
[7]
[8]
CCDC-679188 (for 1), -679189 (for 2), -679190 (for 3), -679191 (for
4), -679192 (for 5), -679193 (for 6a), -679194 (for L1), -679195 (for
L2) contain the supplementary crystallographic data. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.ac.uk/data_request/cif.
[9]
Supporting Information (see also the footnote on the first page of
this article): Figures S1–S3; crystal structures of 1–3 showing π-π
stacking, Figure S4; mass spectrum of 3, Figures S5–S6; NMR
spectra of L1 and L2, Figures S7 and S8; packing structures of 4
and 6a.
[10]
[11]
a) L. Chen, L. K. Thompson, J. N. Bridson, Can. J. Chem.
1992, 70, 2709–2716; b) M. Munakata, L. P. Wu, T. Kuroda-
Sowa, M. Maekawa, Y. Suenaga, S. Nakagawa, J. Chem. Soc.,
Dalton Trans. 1996, 1525–1530; c) M. Heller, W. S. Sheldrick,
Z. Anorg. Allg. Chem. 2003, 629, 1589–1595.
a) K.-M. Park, I. Yoon, J. Seo, J.-E. Lee, J. Kim, K. S. Choi,
O.-S. Jung, S. S. Lee, Cryst. Growth Des. 2005, 5, 1707–1709;
b) J. Y. Lee, S. Y. Lee, J. Seo, C. S. Park, J. N. Go, W. Sim, S. S.
Lee, Inorg. Chem. 2007, 46, 6221–6223; c) T. H. Kim, Y. W.
Shin, S. S. Lee, J. Kim, Inorg. Chem. Commun. 2007, 10, 11–
14.
a) R. D. Adama, M. Huang, S. Johnson, Polyhedron 1998, 17,
2775–2780; b) N. R. Brooks, A. J. Blake, N. R. Champness,
P. A. Cooke, P. Hubberstey, D. M. Proserpio, C. Wilson, M.
Schröder, J. Chem. Soc., Dalton Trans. 2001, 456–465.
Bruker, SMART and SAINT, area detector control and inte-
gration software version 6.22, Bruker Analytical X-ray Instru-
ments, Madison, Wisconsin, 2001.
Acknowledgments
This work was supported by the Korea Research Foundation
(2007-314-C00157). The authors thank Dr. Ki-Min Park for his
advice in the crystallographic work.
[1] a) Comprehensive Supramolecular Chemistry (Eds.: J. L. At-
wood, J. E. D. Davies, D. D. MacNicol, F. Vögtle), Pergamon,
Oxford, 1996, vol. 9; b) L. F. Lindoy, The Chemistry of Macro-
cyclic Complexes, Cambridge University Press, Cambridge,
1989; c) J.-M. Lehn, Supramolecular Chemistry, Concept and
Perspectives, VCH, Weinheim, 1995.
[2] a) H. J. Kim, I. Yoon, S. Y. Lee, K. S. Choi, S. S. Lee, New J.
Chem. 2008, 32, 258–263; b) 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; c) M. R. Song, J.-E. Lee,
S. Y. Lee, J. Seo, K.-M. Park, S. S. Lee, Inorg. Chem. Commun.
2006, 9, 75–78; d) I. Yoon, J. Seo, J.-E. Lee, M. R. Song, S. Y.
Lee, K. S. Choi, O.-S. Jung, K.-M. Park, S. S. Lee, Dalton
Trans. 2005, 2352–2354; e) J. Seo, I. Yoon, J.-E. Lee, M. R.
Song, S. Y. Lee, S. H. Park, T. H. Kim, K.-M. Park, B. G. Kim,
S. S. Lee, Inorg. Chem. Commun. 2005, 8, 916–919.
[12]
[13]
[14]
Bruker, SHELXTL, structure determination program version
6.10, Bruker Analytical X-ray Instruments, Madison, Wiscon-
sin, 2000.
Received: March 19, 2008
Published Online: July 4, 2008
Eur. J. Inorg. Chem. 2008, 3532–3539
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3539