Exo-coordinated discrete and continuous supramolecular silver(I) complexes with thiaoxa-macrocycles

Article abstract of DOI:10.1039/b710581a

Two thiaoxa-macrocycles (L¹: S₃O₂ and L²: S₂O₃) with a dibenzo-subunit were synthesised and structurally characterised by X-ray analysis. Reactions of L¹ and L² with s

Full text of DOI:10.1039/b710581a

View Article Online / Journal Homepage / Table of Contents for this issue
PAPER
www.rsc.org/njc | New Journal of Chemistry
Exo-coordinated discrete and continuous supramolecular silver(I)
complexes with thiaoxa-macrocyclesw
Hyun Jee Kim,a Il Yoon,a So Young Lee,a Kyu Seong Choib and Shim Sung Lee*a
Received (in Durham, UK) 10th July 2007, Accepted 26th September 2007
First published as an Advance Article on the web 9th October 2007
DOI: 10.1039/b710581a
Two thiaoxa-macrocycles (L1: S3O2 and L2: S2O3) with a dibenzo-subunit were synthesised aꢀnd
structurally characterised by X-ray analysis. Reactions of L1 and L2 with silver(I) salts (NO3 and
PF6ꢀ) afforded the respective ligand- and/or anion-directed complexes 1–3 with different
topologies; tetranuclear sandwich [Ag4(L1)2(NO3)4] (1), cyclic tetramer [Ag4(L1)4](PF6)4 (2) and
poly(bicyclic dimer) [Ag(L2)NO3]n (3). The formation of such supramolecular complexes is
discussed in terms of donor or anion effect.
Introduction
The structural modification of macrocyclic ligands and the
careful selection of the metal salt system often lead the
formation of diverse coordination topologies.1 For example,
the versatility of sulfur-containing macrocycles makes them
useful for a range of coordinative products because the sulfur
donor is expected to favour binding towards soft metal ions in
endo- and/or exocyclic mode.2 We have worked on the
assembly of supramolecular coordination architectures based
on the exo-coordination of sulfur-containing macrocycles as
well as their applications.3 A range of mono- and multinuclear
complexes of thiaoxa- or thiaoxaaza-macrocycles with discrete
and continuous types were reported by us2a,3 and other work-
ers.2 We are interested in extending this work in a ligand-
directed approach to construct new supramolecular structures.
In this work, we examine the donor and anion as controlling
factors to direct the assembly of silver(I) complexes. Based on
these considerations, we synthesised thiaoxa-macrocycles L1
and L2. L1 and L2 have a same framework but one sulfur
donor in L1 was replaced by one oxygen atom in L2; the
variation may trigger a change for the resulting complexes. In
the view of silver(I) salt systems employed, it is becoming
apparent that the variation of one donor plays an important
role in the topologies of resulting complexes.
Results and discussion
Synthesis and characterisation of ligands
Synthesis of the ligands began with salicylaldehyde. Dichloride
6 was prepared through dialdehyde 4 and dialcohol 5.4 L1 and
L2 were obtained by coupling reactions for macrocyclisation
from dichloride 6 and corresponding dithiols in the presence of
Cs2CO3 under high dilution condition in reasonable yields
1
(L1: 45%, L2: 41%). The H and 13C NMR spectra together
with elemental analysis and mass spectra were clearly in
agreement with the proposed structures (Scheme 1).
Structures of the macrocycles prepared were also charac-
terised in the solid state by single-crystal X-ray crystallogra-
phy (Fig. 1). Colourless crystals of L1 and L2 suitable for
X-ray analysis were obtained by slow evaporation from the
respective solutions in dichloromethane. Notably, sulfur
a Department of Chemistry (BK21) and Research Institute of Natural
Science, Gyeongsang National University, Jinju 660-701, S. Korea.
E-mail: sslee@gnu.ac.kr; Fax: +8255 7537614;
Tel: +8255 751 6021
b Department of Chemistry, Kyungnam University, Masan 630-701, S.
Korea
w Electronic supplementary information (ESI) available: Fig. S1: 1H
NMR spectra of free L1, L1 + AgNO3 (1.0 equiv.) and L1 + AgPF6
(1.0 equiv.) in CD3CN–DMSO-d6 (1 : 1). Fig. S2. 1H NMR spectra of
free L2 and L2 + AgNO3 (1.0 equiv.) in CD3CN–DMSO-d6 (1 : 1). See
DOI: 10.1039/b710581a
Scheme 1 Synthesis of ligands.
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
258 | New J. Chem., 2008, 32, 258–263

View Article Online
Fig. 1 Molecular structures of (a) L1 and (b) L2. Thermal ellipsoids
are drawn at the 30% probability level.
atoms are oriented in an exodentate fashion. The macrocyclic
ring of L1 is slightly twisted and torsion angles between donor
atoms are indicative of anti arrangements [S1–C–C–S2
172.5(2) and S2–C–C–S3 172.1(2)1]. L2 has a non-folded
configuration with the two exodentate sulfur donors separated
as far as possible; they lie, together with the centroid of
aromatic rings, at the corners of a pseudo-rectangular plane.
The aliphatic segment between donor atoms spans also anti
arrangements with characteristic torsion angles [S1–C–C–O3
179.8(2) and S2–C–C–O3 171.8(3)1].
Scheme 2 Complexes prepared.
Complex syntheses and structural description
In complexation, silver nitrate and hexafluorophosphate were
used to examine the anion effect on the resulting complexes.
Using these reaction systems, we obtained three supramole-
cular complexes 1–3 with different topologies (Scheme 2),
and their structures were characterised by X-ray analysis
(Fig. 2–4).
From the reactions of L1 with silver(I) salts (1: NO3ꢀ and 2:
PF6ꢀ), two complexes 1 and 2 were prepared as follows. Each
colourless precipitate was obtained from L1 with the corre-
sponding silver(I) salts in dichloromethane–methanol and
single crystals of the respective complexes suitable for X-ray
analysis were obtained by vapour diffusion of diethyl ether
into the acetonitrile solution.
The crystal structure of 1 is shown in Fig. 2, with selected
geometric parameters presented in Table 1. The X-ray analysis
revealed that 1 is a unique tetranuclear sandwich-type (4 : 2)
complex [Ag4(L1)2(NO3)4] ꢂ 2CH2Cl2. The asymmetric unit of
1 contains one L1, two silver atoms and two nitrate ions. The
structural unit shown in Fig. 2(a) is generated through inver-
sion symmetry. Ag1 is four-coordinated by two S donors from
one L1, one S donor from adjacent L1 and one bridging
bidentate nitrate ion. Bond angles around Ag1 vary consider-
ably (90.1–150.11). Ag2 is in a distorted trigonal plane with the
coordination sites occupied by the S2 atom, one mono- and
one bridging bidentate nitrate ions, allowing the formation of
a twelve-membered ring composed of four Ag atoms, two S
Fig. 2 Tetranuclear sandwich (4 : 2) structure of 1, [Ag4(L1)2-
(NO3)4] ꢂ 2CH2Cl2: (a) general view, (b) cyclic tetranuclear core, and
(c) space-filling view. Hydrogen atoms and non-coordinating solvent
molecules are omitted for clarity. Thermal ellipsoids are drawn at the
30% probability level. Symmetry operation: (A) ꢀx + 1, ꢀy, ꢀz + 1.
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
New J. Chem., 2008, 32, 258–263 | 259

View Article Online
Fig. 4 Poly(cyclic dimer) structure of 3, [Ag(L2)NO3]n. Hydrogen
atoms are omitted for clarity. Thermal ellipsoids are drawn at the 30%
probability level. Symmetry operations: (A) ꢀx + 1, ꢀy + 1, ꢀz + 1,
(B) ꢀx + 1, ꢀy + 2, ꢀz + 1.
conformation of L1 in 1 is different from that in free L1 in
the view of torsion angles between the neighbouring donor
atoms, the aliphatic segment of S–C–C–S–C–C–S shows an
anti–anti arrangement in free L1, while in 1, it changes to an
anti–gauche arrangement.
To examine the role of anions in the formation of L1
complexes, the reaction was repeated with AgPF6, and the
complex 2 was isolated. The crystal structure of 2 is shown in
Fig. 3, with selected geometric parameters presented in Table 2.
The structure of 2 is more challenging. An X-ray analysis
revealed that 2 is a unique cyclic tetramer (4 : 4) complex
[Ag4(L1)4](PF6)4 ꢂ 4CH2Cl2 (Fig. 3(a)). Since 2 has crystallo-
graphically imposed 4/m symmetry, the asymmetric unit con-
tains half a molecule of L1 and half a silver atom. The silver
atom is in a distorted tetrahedral environment with the
coordination sites occupied by facial mode of three S atoms
from one L1 and one S atom from an adjacent L1 in a bent
arrangement. The continual symmetry operations lead to a
cyclic form, which is made up of four ligands and four silver
atoms with a windmill-like conformation. Consequently, the
repeating S2–Ag1–S2B–Ag1B bonding leads to an octagonal
scaffold with an Ag4S4 core (Fig. 3(c)). The distance between
two opposite silver atoms in the octagonal plane is 6.563(5) A.
The aliphatic segment of S–C–C–S–C–C–S shows an anti–anti
arrangement in free L1, while in 2, it changes to
a
gauche–gauche arrangement. In the packing structure, each
tetramer is arranged in length and breadth with an adjacent
one by long-range interaction of Agꢂ ꢂ ꢂF (3.161 A) through the
Fig. 3 Cyclic tetramer structure of 2, [Ag4(L1)4](PF6)4 ꢂ 4CH2Cl2: (a)
general view, (b) space-filling view, (c) octagonal Ag4S4 core, and (d)
packing view. Hydrogen atoms, non-coordinating anions and solvent
molecules are omitted for clarity. Thermal ellipsoids are drawn at the
30% probability level. Symmetry operations: (A) x, y, ꢀz + 1,
(B) y, ꢀx, z.
ꢀ
bridging PF6 ions such that they form a layered array (Fig.
ꢀ
3(d)). The octagonal cavity is blocked by two trapping PF6
ions above and beneath through the Agꢂ ꢂ ꢂF interactions
Table 1 Selected bond lengths (A) and angles (1) for 1a
atoms, and two bridging bidentate nitrate ions (Fig. 2(b)). In
fact, Ag2 is shifted by 0.70 A towards an adjacent aromatic
ring from the O2S trigonal plane and interacts with two C
atoms (C18A and C19A) in the aromatic ring leading to an Z2-
type cation–p interaction5 [dotted lines, Ag2ꢂ ꢂ ꢂC19A 2.524(2),
Ag2ꢂ ꢂ ꢂC18A 2.728(3) A]. The bond angles around Ag2 show a
Y-shaped geometry [O6–Ag2–S2 127.4(5), S2–Ag2–O3A
126.7(3), O6–Ag2–O3A 79.7(9)1]. Complex 1 adopts an ellip-
tical-cage-like conformation (Fig. 2(c)) but no solvent mole-
cule is included inside. Instead, two non-coordinating
dichloromethane molecules exist in the crystal lattice. The
Ag1–S3A
Ag1–S2
Ag2–O6
Ag2–O3A
2.469(1)
2.811(1)
2.347(2)
2.524(2)
Ag1–S1
Ag1–O5
Ag2–S2
2.475(1)
2.555(2)
2.502(1)
S3A–Ag1–S1
S1–Ag1–O5
S1–Ag1–S2
O6–Ag2–S2
S2–Ag2–O3A
a
150.1(2)
115.0(6)
82.0(2)
127.4(5)
126.7(5)
S3A–Ag1–O5
S3A–Ag1–S2
O5–Ag1–S2
90.2(6)
120.8(2)
78.3(5)
79.7(6)
O6–Ag2–O3A
Symmetry operation: (A) ꢀx + 1, ꢀy, ꢀz + 1.
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
260 | New J. Chem., 2008, 32, 258–263

View Article Online
Table 2 Selected bond lengths (A) and angles (1) for 2a
Ag1–S2B
Ag1–S2
2.532(4)
2.681(4)
Ag1–S1
2.565(3)
S1–Ag1–S1A
S1–Ag1–S2
a
124.5(13)
83.6(7)
S2B–Ag1–S1
S2B–Ag1–S2
113.7(7)
134.3(16)
Symmetry operations: (A) x, y, ꢀz + 1, (B) y, ꢀx, z.
(3.450 A). Some other examples of the cyclic tetrameric
silver(I) complexes [Ag4L4]4+ with dithia- and trithia-macro-
cycles (L) have been reported by us6 and other workers.7
In the reactions of L2, only the crystalline product with
AgNO3 was available. A colourless precipitate was obtained
from the reaction of L2 and AgNO3 in dichloromethane–
methanol. Colourless single crystals of 3 [Ag(L2)NO3]n suita-
ble for X-ray analysis were obtained by vapour diffusion of
diethyl ether into the acetonitrile solution.
Fig. 5 ESI-mass spectrum of 1. The complex solution was prepared
by dissolving L1 and silver(I) nitrate (2 equiv.) in acetonitrile.
The crystal structure of 3 is shown in Fig. 4, with selected
geometric parameters presented in Table 3. An X-ray analysis
revealed that 3 has a one-dimensional double-stranded poly-
meric chain structure. The asymmetric unit contains one L2,
one silver atom and one nitrate ion. The rhomboid
Ag–(NO3)2–Ag units are located at the centre of four L2 and
each cluster core is tetrahedrally coordinated by two sulfur
donors from two adjacent L2 by Ag–S bonds and two oxygen
atoms from two bridging nitrate ions forming an infinite
poly(cyclic dimer) structure. An alternating arrangement of a
pair of macrocycles and a square-dimeric Ag–(NO3)2–Ag unit
forms a large cyclic dimer, corresponding to eighteen-mem-
bered ring. It is noteworthy that the similarities of Sꢂ ꢂ ꢂS
distances between free L2 [7.909(1) A] and 3 [7.878(1) A] as
well as the retention of anti–anti arrangement for the aliphatic
segment of S–C–C–S–C–C–S before and after complexation.
These results suggest that L2 is well preorganised for the
complexation. Some discrete and polymeric species linked
with the square-dimer Ag–(NO3)2–Ag unit have been reported
previously.8 To our knowledge, however, 3 is the first example
in which the sulfur-containing ligand is employed for the
construction of the Ag–(NO3)2–Ag linking unit based species.
This result also shows that the nitrate anion as a second
coordinating species has a remarkable influence on the struc-
ture and topology of the assembled product.
1430.7) (Fig. 5). The results show that species 1 also exist in
solution state as a stable form.
In addition, comparative NMR studies were carried out for
the complex system (Fig. S1 and S2, ESIw). In the case of
silver(I) complexes, the peaks for methylene protons adjacent
to the sulfur donors show larger downfield shifts suggesting
that the silver(I) is strongly coordinated by sulfur donors, and
the oxygen atoms interact with the silver(I) weakly, similar to
the case in the solid state.
Conclusions
The preparation and structural characterisation of three types
of silver(I) complexes 1–3 derived from thiaoxa-macrocycles
have been presented. The versatility of results is emphasised on
the influences of the variation of anions and donor atoms on
the respective supramolecular complexes. For example, com-
paring the structures between 1 and 2 afforded a good case for
ꢀ
the anion effect on the frameworks of complexes. The NO3
ions in 1ꢀpossessing stronger coordination or donor ability
than PF6 occupy the coordination site bridging two silver
atoms or terminating the structure and, consequently, allow
the formation of high nuclear species. In case of 2, however,
the preference of assembly of the cyclic tetramer is due to the
ꢀ
weaker affinity of PF6 towards silver atom which leads the
Electrospray ionisation (ESI) mass study
anion to be excluded from the coordination sphere. On going
from 1 to 3, we observed that replacement of one sulfur to
oxygen donor induced the formation of an infinite structure
because of the reduced chance of Ag–S bond formation. It is
concluded that these results show donors and anions have a
great influence on the structures of the resulting supramole-
cular complexes.
We also carried out ESI-mass experiments for 1 in solution
state to compare with that in solid state. The mass spectrum of
L1 with a mixture of two equivalent silver(I) nitrate was
dominated by mono- to tetranuclear species such as
[Ag(L1)2]+ (m/z 921.9), [Ag2(L1)2(NO3)]+ (m/z 1090.9),
[Ag3(L1)2(NO3)2]+ (m/z 1261.8), [Ag4(L1)3(NO3)3]+ (m/z
Table 3 Selected bond lengths (A) and angles (1) for 3a
Experimental
Ag1–S2A
Ag1–O4B
2.454(1)
2.503(3)
Ag1–S1
Ag1–O4
2.463(1)
2.576(2)
General remarks
Chemical reagents and solvents were purchased commercially
and used as received without further purification. Infrared
spectra were measured with a Mattson Genesis Series FT-IR
spectrophotometer, and the NMR spectra were recorded with
S2A–Ag1–S1
151.2(1)
S2A–Ag1–O4B
118.9(1)
a
Symmetry operations: (A) ꢀx + 1, ꢀy + 1, ꢀz + 1, (B) ꢀx + 1, ꢀy
+ 2, ꢀz + 1.
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
New J. Chem., 2008, 32, 258–263 | 261

View Article Online
a Bruker 300 MHz spectrometer. Mass spectra were obtained
on a QTRAP-3200 spectrometer at the Central Laboratory of
Gyeongsang National University.
1594, 1496, 1450, 1414, 1352, 1300, 1237, 1098, 1022, 750, 668
cmꢀ1. 1H NMR (300 MHz, CDCl3): d 7.32–6.87 (m, 8 H, Ar),
4.24 (t, 4 H, OCH2), 3.81 (s, 4 H, ArCH2), 3.40 (t, 4 H,
OCH2CH2S) 2.61 (t, 4 H, SCH2CH2O), 2.40 (t, 2 H, OCH2C-
H2CH2O) ppm. 13C NMR (75 MHz, CDCl3): d 156.33, 131.00,
128.39, 127.70, 121.12, 111.18, 70.69, 64.38, 30.26, 29.84, 29.29
ppm. ESI-MS m/z 391.3 (MH+).
Synthesis and characterisation of L1
Cesium carbonate (7.47 g, 23.0 mmol) was dissolved in DMF
(1000 cm3) in a 3-liter round-bottom flask. 2-Mercaptoethyl
sulfide (2.36 g, 12.3 mmol) and 2,20-(propyleneoxy)bis(benzyl
chloride) (4.0 g, 12.3 mmol) was dissolved in DMF (30 cm3)
and this solution was added to a 50-cm3 glass syringe. Under a
nitrogen atmosphere, the contents of the syringe was added
1
[Ag4(L )2(NO3)4] 2CH2Cl2 (1)
.
A colourless precipitate was obtained by mixing of L1 and
AgNO3 (2 equiv.) in dichloromethane–methanol. Colourless
crystals were obtained by vapour diffusion of diethyl ether into
the acetonitrile solution. Yield: 60%. Mp (decomp.) 4140 1C.
[Ag4(L1)2(NO3)4] ꢂ 2CH2Cl2: calc.: C 31.79, H 3.39, S 11.57, N
3.37; found: C 32.02, H 3.47, S 11.89, N 3.40%. IR (KBr)
2942, 1597, 1493, 1458, 1390 (NO3ꢀ), 1294, 1248, 1104, 1047,
755. ESI-MS m/z 1430.7 [Ag4(L1)2(NO3)3]+.
dropwise (a rate of 0.6 cm3
h
ꢀ1) into a DMF solution of
Cs2CO3 at 45–50 1C for 50 h. The reaction mixture was kept
for a further 10 h with rapid stirring, allowed to cool to room
temperature, then filtered. The filtrate was evaporated and the
residue was partitioned between water and dichloromethane.
The aqueous phase was separated and extracted with two
further portions of dichloromethane. The combined organic
phases were dried with anhydrous sodium sulfate and then
evaporated to dryness. Flash column chromatography on
silica gel using 50% dichloromethane–n-hexane as the eluent
led to the isolation of L1 as a colourless crystalline product in
45% yield. Mp 110–112 1C. C21H26O2S3 (406.62): calc.: C
62.03, H 6.44 S 23.66; found: C 62.42, H 6.10, S 23.96%. IR
(KBr) 2931, 2871, 1602, 1496, 1447, 1415, 1286, 1237, 1093,
1047, 756 cmꢀ1. 1H NMR (300 MHz, CDCl3): d 7.34–6.88 (m,
8 H, Ar), 4.26 (t, 4 H, OCH2), 3.82 (s, 4 H, ArCH2), 2.54 (m, 8
H, SCH2CH2), 2.38 (m, 2 H, OCH2CH2CH2O) ppm. 13C
NMR (75 MHz, CDCl3); d 156.34, 131.07, 128.50, 126.90,
121.06, 111.11, 64.25, 32.91, 31.29, 29.71, 29.36 ppm. ESI-MS
m/z 407.9 (MH+).
[Ag4(L1)4](PF6)4 4CH2Cl2 (2)
.
A colourless precipitate was obtained by mixing of equimolar
amounts of L1 and AgPF6 in dichloromethane–methanol.
Colourless crystals were obtained by vapour diffusion of
diethyl ether into the acetonitrile solution. Yield: 70%. Mp
(decomp.) 4169 1C. [Ag4(L1)4](PF6)4 ꢂ 4CH2Cl2: calc.: C
35.50, H 3.79, S 12.92; found: C 35.13, H 3.69, S 13.11%.
IR (KBr) 2866, 2365, 1599, 1493, 1455, 1240, 1104, 1060, 845
(PF6ꢀ), 758, 734, 559 cmꢀ1. ESI-MS m/z 513.6 [Ag4(L1)4]4+
.
[Ag(L2)NO3]n (3)
A colourless precipitate was obtained from the reaction of L2
with AgNO3 (1 equiv.) in dichloromethane–methanol. Colour-
less single crystals were obtained by vapour diffusion of diethyl
ether into the acetonitrile solution. Yield: 30%. Mp (decomp.)
4195 1C. [Ag(L2)NO3]: calc.: C 45.01, H 4.68, N 2.50, S 11.44;
found C 45.36, H 4.58, N 2.62, S 11.48%. IR (KBr) 2931,
2877, 1594, 1496, 1387 (NO3ꢀ), 1289, 1245, 1123, 845,
Synthesis and characterisation of L2
The synthetic procedure was almost the same as for L1 except
for the use of 2-Mercaptoethyl ether. Flash column chroma-
tography (SiO2; n-hexane–ethyl acetate 9 : 1) afforded the
product as a white solid in 41% yield. Mp 99–101 1C.
C21H26O3S2 (390.56): calc.: C 64.58, H 6.71, S 16.42; found:
C 64.30, H 6.38, S 16.30%. IR (KBr) 2931, 2861, 1904, 1787,
761 cmꢀ1
.
Table 4 Crystal and experimental data
L1
L2
1
2
3
Formula
Mr
T/K
Crystal system
Space group
Z
a/A
b/A
c/A
C
406.60
298(2)
21H26O2S3
C21H26O3S2
390.54
173(2)
C44H56Ag4Cl4N4O16S6 C88H112Ag4Cl8F24O8P4S12
C21H26Ag1N1O6S2
560.42
298(2)
Triclinic
ꢀ
P1
1662.57
173(2)
Triclinic
P1
1
2977.46
173(2)
Tetragonal
P4/mnc
2
Orthorhombic Monoclinic
Cc
ꢀ
Pca21
8
4
2
13.2221(9)
12.4315(8)
25.7337(2)
90
90
90
4229.9(5)
1.277
56.68
0.0467
0.1011
9258
11.8755(7)
11.3829(6)
15.7149(9)
90
108.787(1)
90
2011.1(2)
1.290
52.74
0.0379
0.1226
2780
9.5230(6)
12.0312(7)
14.1546(8)
73.512(1)
86.303(1)
67.543(1)
1435.4(2)
1.923
52.74
0.0239
0.0547
5745
0.0166
15.8399(1)
15.8399(1)
22.847(3)
90
90
90
5732.5(9)
1.725
52.04
0.0806
0.1821
2913
8.8853(1)
11.1795(1)
12.8220(2)
70.863(2)
87.579(2)
71.115(2)
1135.6(2)
1.639
52.72
0.0287
0.0742
4564
0.0355
a/1
b/1
g/1
V/A3
Dc/g cmꢀ3
2ymax/1
R
wR
No. reflections used [I 4 2s(I)]
Rint
0.0385
0.0318
0.2592
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
262 | New J. Chem., 2008, 32, 258–263

View Article Online
X-Ray crystallography
2004, 12, 2086; (d) F. Contu, F. Dermartin, F. A. Devillanova,
A. Garau, F. Isaia, V. Lippolis, A. Salis and G. Verani,
J. Chem. Soc., Dalton Trans., 1997, 4401; (e) M. A. Watzky,
D. Waknine, M. J. Heeg, J. F. Endicott and L. A.
Ochrymowyzc, Inorg. Chem., 1993, 32, 4882; (f) A. J. Blake, M.
All data were collected on a Bruker Smart diffractometer
equipped with a graphite monochromated Mo-Ka (l =
0.71073 A) 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 SAINT.9
The structure was solved by direct methods and refined by full-
matrix least-squares methods on F2 for all data using
SHELXTL software.10 The non-hydrogen atoms were refined
anisotropically. Relevant crystal data collection and refine-
ment data for the crystal structures of L1, L2, 1, 2 and 3 are
summarised in Table 4.
A. Halcrow and M. Schroder, J. Chem. Soc., Dalton Trans., 1992,
¨
Chem. Commun., 1992, 1074; (h) A. J. Blake, R. O. Gould, C.
¨
2803; (g) A. J. Blake, G. Reid and M. Schroder, J. Chem. Soc.,
Radek and M. Schroder, J. Chem. Soc., Chem. Commun., 1994,
985.
¨
3 (a) J. Seo, M. R. Song, J.-E. Lee, S. Y. Lee, I. Yoon, K.-M. Park,
J. Kim, J. H. Jung, S. B. Park and S. S. Lee, Inorg. Chem., 2006,
45, 952; (b) M. R. Song, J.-E. Lee, S. Y. Lee, J. Seo, K.-M. Park
and S. S. Lee, Inorg. Chem. Commun., 2006, 9, 75; (c) I. Yoon,
J. Seo, J.-E. Lee, M. R. Song, S. Y. Lee, K. S. Choi, O.-S. Jung,
K.-M. Park and S. S. Lee, Dalton Trans., 2005, 2352; (d) 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 and S. S. Lee, Inorg. Chem. Commun.,
2005, 8, 916.
4 Y. A. Ibrahim, A. H. M. Elwahy and G. M. M. Elkareish, J. Chem.
Res. (S), 1994, 11, 414.
CCDC reference numbers 645646 (for L1), 645647 (for L2),
5 (a) J. C. Ma and D. A. Dougherty, Chem. Rev., 1997, 97, 1303; (b)
R. Ungaro, A. Casnati, F. Ugozzoli, A. Pochini, J.-F. Dozol, C.
Hill and H. Rouquette, Angew. Chem., Int. Ed. Engl., 1994, 33,
1506; (c) A. Ikeda and S. Shinkai, J. Am. Chem. Soc., 1994, 116,
3102; (d) J. Y. Lee, J. Kwon, C. S. Park, J.-E. Lee, W. Sim, J. S.
Kim, J. Seo, I. Yoon, J. H. Jung and S. S. Lee, Org. Lett., 2007, 9,
493.
645642 (for 1), 645643 (for 2) and 645644 (for 3).
For crystallographic data in CIF or other electronic format
see DOI: 10.1039/b710581a
Acknowledgements
6 S. Y. Lee, J. Seo, I. Yoon, C.-S. Kim, K. S. Choi, J. S. Kim and S.
S. Lee, Eur. J. Inorg. Chem., 2006, 3525.
7 (a) H. A. Jenkins, S. J. Loeb and A. M. I. Riera, Inorg. Chim. Acta,
1996, 246, 207; (b) T. Yamaguchi, F. Yamazaki and T. Ito, Acta
Crystallogr., Sect. C, 2002, 58, m213; (c) U. Heinzel and R. Mattes,
Polyhedron, 1991, 10, 19.
This work was supported by KOSEF (Grant R01-2004-000-
10321-0). Authors thank Dr Ki-Min Park for his advice in the
crystallographic work.
8 (a) D. Fortin, M. Drouin, P. D. Herring, D. A. Summers and R. C.
Thompson, Inorg. Chem., 1999, 38, 1253; (b) F. Bachechi, A.
Curini, R. Galassi, A. Macchioni, B. R. Pietroni, F. Ziarelli and
C. Zuccaccia, J. Organomet. Chem., 2000, 593, 392; (c) J. T.
Sampanthar and J. J. Vittal, Cryst. Eng., 2000, 3, 117; (d) J. H.
Meiners. J. C. Clardy and J. G. Verkade, Inorg. Chem., 1975, 14,
632; (e) F. Caruso, M. Camalli, H. Rimml and L. M. Venanzi,
Inorg. Chem., 1995, 34, 673.
9 Bruker, SMART and SAINT, Area Detector Control and Integra-
tion Software Ver. 6.22, Bruker Analytical X-ray Instruments:
Madison, WI, 2001.
10 Bruker, SHELXTL, Structure Determination Programs Ver. 6.10,
Bruker Analytical X-ray Instruments, Madison, WI, 2000.
References
1 (a) Comprehensive Supramolecular Chemistry, ed. J. L. Atwood, J.
E. D. Davies, D. D. MacNicol and F. Vogtle, Pergamon, Oxford,
¨
1996, vol. 9; (b) C. B. Aakeroy and A. S. Borovik, Crystal
¨
Engineering, Coord. Chem. Rev., 1999, 183, 1; (c) E. Weber, Design
of Organic Solids, Top. Curr. Chem., 1998, 198; (d) Crystal
Engineering: The Design of Organic Solids, ed. G. R. Desiraju,
Elsevier, Amsterdam, 1989.
2 (a) Y. Habata, J. Seo, S. Otawa, F. Osaka, K. Noto and S. S. Lee,
Dalton Trans., 2006, 2202; (b) D. E. Janzen, L. F. Mahne, D. G.
VanDerveer and G. J. Grant, Inorg. Chem., 2005, 44, 8182; (c) M.
Vetrichelvan, Y.-H. Lai and K. F. Mok, Eur. J. Inorg. Chem.,
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008
New J. Chem., 2008, 32, 258–263 | 263