The role of the metal connectors AgNO3, Cu2i2 and CuCl2 in co-ordination-polymer formation using the N2S2 ditopic ligand 1,4-bis(2-py ridylmethy Isulfanylmethyl)benzene

Article abstract of DOI:10.1039/a909601i

The extended-reach ligand l,4-bis(2-pyridylmethylsulfanylmethyl)benzene(L) was prepared by base coupling of 2-(chloromethyl)pyridinehydrochloride and 1,4-bis(sulfanylmethyl)benzene. This new ligand was treated with metal connectors AgNO3, CuX(X = Cl, Br or I) and CuQ2 to give co-ordination polymers. The crystal structures of [Ag₂(L)(NO₃)₂]_r, [Cu₂(L)I₂]_x and [Cu(L)Cl2]_n were determined. Comparison of the structures showed that the anion influenced the mode of metal binding with chelating or bridging modes being observed. The anion also influenced the nature of the packing, with the silver polymer forming a three-dimensional array containing clathrated water ladders while the copper polymers existed as related one-dimensional polymers. The remarkable feature of these structures is that while the silver polymer showed extensive intermolecular interactions, the copper polymers, despite the prevalence of aromatic rings, each displayed only one type of CH/rc interaction. The Royal Society of Chemistry 2000.

Full text of DOI:10.1039/a909601i

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The role of the metal connectors AgNO3, Cu2I2 and CuCl2 in
co-ordination-polymer formation using the N2S2 ditopic ligand
1,4-bis(2-pyridylmethylsulfanylmethyl)benzene†
Lyall R. Hanton* and Kitty Lee
Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand.
E-mail: lhanton@alkali.otago.ac.nz
Received 6th December 1999, Accepted 18th February 2000
The extended-reach ligand 1,4-bis(2-pyridylmethylsulfanylmethyl)benzene (L) was prepared by base coupling
of 2-(chloromethyl)pyridinehydrochloride and 1,4-bis(sulfanylmethyl)benzene. This new ligand was treated with
metal connectors AgNO3, CuX (X = Cl, Br or I) and CuCl2 to give co-ordination polymers. The crystal structures
of [Ag2(L)(NO3)2]∞, [Cu2(L)I2]∞ and [Cu(L)Cl2]∞ were determined. Comparison of the structures showed that the
anion influenced the mode of metal binding with chelating or bridging modes being observed. The anion also
influenced the nature of the packing, with the silver polymer forming a three-dimensional array containing
clathrated water ladders while the copper polymers existed as related one-dimensional polymers. The remarkable
feature of these structures is that while the silver polymer showed extensive intermolecular interactions, the
copper polymers, despite the prevalence of aromatic rings, each displayed only one type of CH/π interaction.
Introduction
Recently the use of thioether–pyridine moieties in the prepar-
ation of new extended-reach ligands has been investigated for
the construction of metallosupramolecular arrays.1–3 The co-
ordinating abilities of these donors are ideally suited to forming
complexes with the metals most often used in such networks.4 A
or I) and CuCl2. The crystal structures of three co-ordination
number of complexation studies has investigated the influence
of systematic variations of ligand structure on the overall
molecular architecture.1,2,5 For example, the three isomeric
bis(2-pyridylsulfanylmethyl)benzenes have been shown to
bridge two or more silver() centres.2 The ortho and meta iso-
mers form one-dimensional co-ordination polymers while the
para isomer forms a metallocyclic dimer.
polymers are described and compared. Two different types of
metal binding modes, chelating and bridging, are observed
(Scheme 1).
We decided to investigate the effect of the variation of metal
connector on co-ordination-polymer formation using a related
but conformationally more flexible ligand based on a para-
substituted benzene linker with two thioether–pyridine arms.
The ligand provides two separate donor regions and this
arrangement may allow for the unconstrained formation of
dimeric or polymeric complexes upon reaction with metal con-
nectors. The co-ordination preference of the metal connector
has an enormous influence in controlling the nature of the co-
ordination polymer. For example, the major factor determining
the mode of co-ordination for 2,2Ј-dimethyl-4,4Ј-bipyrimidine
was found to be the type of metal ion used.6 Copper() was
found only in a bidentate bridging mode while more than one
co-ordination mode was identified for CuI and AgI. When
AgNO3 was used as a connector, NO3Ϫ played a dominant role
in network connectivity. Further, other studies have shown that
more subtle effects such as the nature of the anion7 or inter-
molecular π–π stacking8 or M–X ؒ ؒ ؒ H9 interactions can also
have a significant influence on the co-ordination polymer
formed.
Scheme 1 Schematic diagram of the bonding modes for the metal
connectors in complexes 1, 3 and 5.
We now report the synthesis of a new extended-reach ligand
1,4-bis(2-pyridylmethylsulfanylmethyl)benzene (L) and reac-
tions with the neutral metal connectors AgNO3, Cu2X2 (X = Br
Results and discussion
Ligand and complex synthesis
The ligand 1,4-bis(2-pyridylmethylsulfanylmethyl)benzene (L)
was prepared by the base coupling of 2-(chloromethyl)pyridine-
† Dedicated to Dr Malcolm Gerloch on the occasion of his retirement
from the University of Cambridge, with best wishes for life in Australia.
DOI: 10.1039/a909601i
J. Chem. Soc., Dalton Trans., 2000, 1161–1166
This journal is © The Royal Society of Chemistry 2000
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hydrochloride10 and 1,4-bis(sulfanylmethyl)benzene11 in a 2:1
molar ratio. Purification was accomplished by recrystallisation
from CH2Cl2–light petroleum (bp 40–60 ЊC) to give a fawn air-
stable crystalline solid in moderate yield. The ligand L reacts
readily with the metal salts AgNO3, CuX (X = Cl, Br or I) and
CuCl2 to give complexes in good yield. A 1:2 molar ratio of L
and AgNO3 or CuX (X = Br or I) gave the products 1, 2 and 3
as analytically pure white or cream powders, respectively. The
products were insoluble in most common solvents suggesting
the formation of co-ordination polymers. In contrast, the
product from the analogous reaction with CuCl did not precipi-
tate from solution and appeared unstable. Microanalytical
results for the product isolated from this reaction were erratic
and inconclusive. Reaction of L and CuCl2 in a 1:2 molar ratio
produced 4 as a green solid which analysed with a 1:2 ligand:
metal ratio. This product was also insoluble in most common
solvents suggesting the formation of a co-ordination polymer
with formula [Cu2(L)Cl4]∞. However crystallisation by slow dif-
fusion of the two precursors over a week consistently produced
strongly dichroic green/orange crystals which analysed with a
1:1 metal:ligand ratio (5). These crystals were suitable for a
structure analysis. Bulk reaction of L and CuCl2 in a 1:1 molar
ratio also produced 5 as a microanalytically pure green powder
in good yield.
Fig. 1 Perspective view (crystallographic numbering) of the co-
ordination environment of complex 1. Thermal ellipsoids are drawn at
the 50% probability level. Selected bond lengths (Å) and angles (Њ):
Ag(1)–N(1) 2.277(2), Ag(1)–O(2) 2.500(2), Ag(1)–S(1I) 2.5048(9) and
Ag(1)–O(1) 2.567(2); N(1)–Ag(1)–O(2) 94.42(7), N(1)–Ag(1)–S(1I)
132.36(5), O(2)–Ag(1)–S(1I) 132.46(5), N(1)–Ag(1)–O(1) 123.92(7),
O(2)–Ag(1)–O(1) 50.52(6) and S(1I)–Ag(1)–O(1) 97.30(5) (symmetry
code: I Ϫx, Ϫy Ϫ 1, Ϫz).
The solid-state electronic spectra of complexes 2, 3 and 5 are
all very similar in the near-infrared region suggesting an iso-
structural arrangement of the ligand. The two copper() com-
₁
plexes 4 and 5 show different broad d–d features (ν ≈ 10 000
₂

cmϪ1) in the region 20 000 to 6 250 cmϪ1. The spectrum of the
1:1 compound 5 shows two bands of similar intensity at 13 000
and 9 260 cmϪ1 consistent with an asymmetric co-ordination
environment about the copper() connector.12 However, the 1:2
compound 4 displays only a single symmetric band at 10 500
cmϪ1 suggesting a more regular environment about the CuII. All
the polymers show a number of broad charge-transfer bands in
the UV region.13 Comparisons of the IR spectra show the same
trends as above with 2, 3 and 5 having almost identical spectra
while 1 and, in particular, 4 display a number of differences.
Structure of [Ag2(L)(NO3)2ؒ4H2O]∞ 1
Colourless rectangular crystals suitable for structure analysis
were grown by slow evaporation over a number of weeks from a
dilute MeCN solution of complex 1. In the structure of complex
1 the asymmetric unit consists of a silver() ion, half a ligand L,
a nitrate anion and two water molecules (Fig. 1). The silver()
ion adopts a distorted tetrahedral arrangement. It is bound to
one pyridine donor of a ligand L and one thioether donor of a
second symmetry related ligand, thus forming the basis of
a polymeric link between two ligands (Fig. 2). There are no
interactions between the AgI and the adjacent potentially
chelating thioether donor [Ag ؒ ؒ ؒ S 3.1652(9) Å].2 Two O
atoms of the nitrate anion bind symmetrically to complete
the co-ordination sphere about the AgI. A second symmetry
generated silver ion binds the remaining donors of each
arm to form a puckered 10-membered metallocyclic ring
Fig. 2 (a) A view of two adjacent chains of complex 1 showing weak
Ϫ
Ϫ
C(pyridine)–H ؒ ؒ ؒ ONO2 and strong HO–H ؒ ؒ ؒ ONO2 interactions
and the corrugated ladders of water molecules running into the page.
(b) View along a corrugated ladder of water molecules.
[–Ag(1)–S–C–C–N–Ag(2)–S–C–C–N–]. Within the 10-mem-
bered ring the donors of each arm bridge two silver() centres
[Ag ؒ ؒ ؒ Ag 4.541(1) Å]. The arms of the ligand lie in a trans
configuration as a result of a centrosymmetric relationship with
respect to the central arene ring. The ligand is folded such that
the three rings lie in a stepped fashion, essentially parallel to
each other [angle between the planes: 9.0Њ]. All silver-donor
bond distances are within accepted values.2,14 The co-ordination
of the Ag to two O atoms of the nitrate anion causes the tetra-
hedral bond angles about Ag to be severely distorted [O(1)–Ag–
O(2) 50.52(6), N(1)–Ag–S(1I) 132.36(5)Њ]. The 10-membered
rings, formed by two silver connectors and two different ligand
arms, are joined by the central arene ring of the ligand to form
a one-dimensional polymeric chain approximately along the
b axis. Surprisingly, the related ligand 1,4-bis(2-pyridylsulfanyl-
methyl)benzene forms a metallocyclic dimer albeit with a 1:1
ligand to Ag ratio.2
The chains stack directly on top of each other and are held
Ϫ
together by strong intermolecular interactions {Ag ؒ ؒ ؒ NO3
[Ag ؒ ؒ ؒ N 3.222(2); Ag ؒ ؒ ؒ O 2.833(2), 2.996(3) Å], S ؒ ؒ ؒ NO3
Ϫ
[S ؒ ؒ ؒ O 3.166(2) Å] and Ag ؒ ؒ ؒ H 3.3447(7) Å} to form a
two-dimensional sheet. In addition, weak C–H ؒ ؒ ؒ arene
[H ؒ ؒ ؒ arene(centroid) 2.84 Å] interactions are also present
due to the methylene hydrogens of xylyl moieties being slightly
positively charged.15
These sheets form a three-dimensional polymer via two
types of intermolecular interactions. First, there are weak
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Fig. 3 Perspective view (crystallographic numbering) of the co-
ordination environment of complex 3. Thermal ellipsoids are drawn at
the 50% probability level. Selected bond lengths (Å) and angles (Њ): I(1)–
Cu(1) 2.5839(7), Cu(1)–I(1I) 2.6406(8), Cu(1)–N(1) 2.073(5), Cu(1)–
S(1) 2.374(2) and Cu(1) ؒ ؒ ؒ Cu(1I) 2.531(1); Cu(1)–I(1)–Cu(1I) 57.93(3),
N(1)–Cu(1)–S(1) 85.3(1), N(1)–Cu(1)–I(1) 109.9(1), S(1)–Cu(1)–I(1)
117.82(4), N(1)–Cu(1)–I(1I) 116.6(1), S(1)–Cu(1)–I(1I) 98.97(4) and
I(1)–Cu(1)–I(1I) 122.07(3) (symmetry code: I Ϫx ϩ 1, Ϫy ϩ 1, Ϫz ϩ 1).
Fig. 5 Perspective view (crystallographic numbering) of the co-
ordination environment of complex 5. Thermal ellipsoids are drawn at
the 50% probability level. Selected bond lengths (Å) and angles (Њ):
Cu(1)–N(1) 2.043(2), Cu(1)–Cl(1) 2.3273(5) and Cu(1)–S(1) 2.7624(6);
N(1)–Cu(1)–Cl(1I) 91.05(4), N(1)–Cu(1)–Cl(1) 88.95(4), N(1)–Cu(1)–
S(1I) 101.51(4), N(1)–Cu(1)–S(1) 78.49(4), Cl(1)–Cu(1)–S(1) 92.47(2)
and Cl(1)–Cu(1)–S(1I) 87.53(2), (symmetry code: I Ϫx ϩ 1, Ϫy ϩ 1,
Ϫz ϩ 1).
Fig. 4 View of complex 3, with hydrogens omitted, showing the layer-
like arrangement of adjacent polymeric chains and the one ring offset
between chains.
Fig. 6 View of complex 5, with hydrogens omitted, showing the layer-
like arrangement of adjacent polymeric chains and the two rings offset
between chains.
Ϫ
C(pyridine)–H ؒ ؒ ؒ NO3 [H ؒ ؒ ؒ O 2.577(2) Å] interactions
between adjacent sheets (Fig. 2a). Secondly, corrugated ladders
of strongly hydrogen-bound water molecules (H2O)∞ (Fig. 2b)
lie between the sheets, clathrated within channels provided by
the central para-substituted ring of L. The O–H ؒ ؒ ؒ O distances
are comparable to those found in ice16 [O–H ؒ ؒ ؒ O distances
and angles 2.00(3) Å, 167(3)Њ; 2.21(2) Å, 159(2)Њ and 2.03(2) Å,
173(2)Њ]. These ladders are strongly hydrogen-bound to nitrate
anions on adjacent sheets [H ؒ ؒ ؒ O 2.04(3) Å] (Fig. 2a).
distorted and is most likely due to the NS bite angle constraint
imposed by the chelating mode of the ligand [N(1)–Cu(1)–S(1)
85.3(1), N(1)–Cu(1)–I(1) 109.9(1), S(1)–Cu(1)–I(1I) 98.97(4)Њ].
These CuI2Cu moieties connect the ligands to form a one-
dimensional zigzag polymeric chain which propagates along the
1 1 0 diagonal axis. The bridging iodides lie above and below the
planes of the pyridine rings. The zigzag chains lie side-by-side
in a layer-like arrangement, diagonally offset by one ring so
that pyridine rings from adjacent chains appear to be overlaid.
However, inter-ring distances are too large (5.25 Å) to permit
π–π interactions (Fig. 4). These layers lie on top of each other
such that the directions of the chains within each layer are
orthogonal to those in adjacent layers. While no signifi-
cant interactions exist between the chains in the layer-like
arrangement, there are C(methylene)–H ؒ ؒ ؒ pyridine inter-
actions between orthogonally arranged chains in adjacent
layers. The distance of 2.75 Å is within the mean distance of
2.77 0.10 Å for this type of CH/π interaction.20 There are no
other significant interactions within or between the layers
suggesting that 3 can be considered a one-dimensional polymer.
Structure of [Cu2(L)I2]∞ 3
Yellow rhombic crystals suitable for structure analysis were
grown by the slow diffusion over several weeks of MeCN solu-
tions of the two reactants. In the structure of complex 3 the
asymmetric unit consists of a copper() ion, half a ligand and
an iodide counter ion. The CuI adopts a distorted tetrahedral
co-ordination sphere and is chelated by a pyridine and a
thioether donor from a ligand arm and is bound to a bridging
iodide counter ion (Fig. 3). A symmetry related iodide com-
pletes the co-ordination sphere about the CuI. Both of these
iodides are bound to a symmetry related CuI thus forming a
CuI2Cu connector between two ligands as the basis of a poly-
meric chain (Fig. 4). The formation of CuI2Cu connections,
rather than ones based on more complex CuI motifs, is consist-
ent with the use of a more sterically demanding ligand.17
The ligand L is folded in a manner similar to that in complex
1 such that the three rings lie in a stepped fashion [angle
between the planes: 19.1Њ]. The copper()–donor bond distances
are all within normal values.18 Within the CuI2Cu connectors
the copper() centres are separated by a relatively short distance
of 2.531(1) Å, which is significantly shorter than most other
reported values.19 The tetrahedral geometry about each CuI is
Structure of [Cu(L)Cl2]∞ 5
The asymmetric unit consists of half a copper() ion, half
a ligand L and a bound chloride counter ion (Fig. 5). The
CuII lies on a centre of symmetry and adopts a distorted
octahedral co-ordination sphere containing a pyridine and a
thioether donor from a chelated ligand arm, a chloride counter
ion and the three symmetry-related donors. Thus, it forms a
connector between two ligands giving a one-dimensional co-
ordination polymer (Fig. 6).
J. Chem. Soc., Dalton Trans., 2000, 1161–1166
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The ligand L is again folded in a stepped configuration [angle
between the planes: 24.9Њ]. The Cu–N and Cu–Cl distances are
all within normal values.18 Interestingly, it is the Cu–S distances
[Cu(1)–S(1) 2.7624(6) Å] rather than the Cu–Cl distances that
are slightly longer than normal values for the Jahn–Teller dis-
torted copper() centre.12,21 These longer Cu–S distances are
made possible by the non-ideal NS chelate-bite angle [N(1)–
Cu(1)–S(1) 78.49(4)Њ] enforced by the ligand. The other bond
angles about the CuII are within normal values [N(1)–Cu(1)–
Cl(1) 88.95(4), S(1)–Cu(1)–Cl(1) 92.47(2)]. This asymmetrical
co-ordination environment is consistent with the two d–d broad
bands observed in the electronic spectrum of 5. In a similar
fashion to that in 3, the metal centre links two ligands together
to form a one-dimensional zigzag polymeric chain which
propagates along the 1 1 0 diagonal axis. The zigzag chains lie
side-by-side to form a layer and are diagonally offset by two
rings so that pyridine rings overlay with arene rings from
adjacent chains through very weak edge-to-face π interactions.
The C(pyridine)–H ؒ ؒ ؒ para-ring distance of 2.94 Å is at the
conventional van der Waals limit (ca. 2.9 Å) and considerably
longer than the average C(arene)–H ؒ ؒ ؒ arene distance of
2.76 0.10 Å.20 However, it has been suggested that the CH/π
interaction may be effective at distances beyond the van der
Waals limit.20 The two rings are inclined at 24.9Њ to each other.
These layers are overlaid such that alternate layers are orthog-
onal to each other with respect to the direction of the chains
within the layers. There are no significant interactions between
the chains of the adjacent layers and 5 can be considered as a
one-dimensional polymer.
Fig. 7 (a) View of the overlaid asymmetric units of complexes 3 (solid
lines) and 5 (open lines). (b) View of the overlaid metal connectors of 3
(solid lines) and 5 (open lines) showing the displacement caused by the
different metal connectors.
Comparison
Despite the flexibility of the –CH2–S–CH2– arms, the ligand
adopts a very similar trans-stepped conformation in all three
structures. Upon co-ordination two different binding modes are
found. In the case of the silver polymer 1 each polymeric link is
formed by a double AgNO3 connection in which the ligand
arms bridge rather than chelate the metal centres. Chelation of
the ligand, which itself has a small bite angle, is probably dis-
prevalence of aromatic rings and Cu–X moieties there are no
significant π–π or Cu–X ؒ ؒ ؒ H interactions. These structures,
therefore, can be regarded as one-dimensional polymers. By
comparison 1 can be considered to be a three-dimensional
polymer as a result of extensive intermolecular interactions
involving the NO3Ϫ anion.
Ϫ
favoured in 1 by the symmetrical binding of the chelated NO3
anion as this would lead to an unfavourably distorted geometry
about the AgI. The NO3Ϫ anion has a major role in controlling
the stacking of the chains to form sheets and the connectivity
between the sheets.6 Throughout the structure of 1 all the
Experimental
General
Ϫ
chains are aligned in the same direction. The NO3 anion and
The precursors 2-(chloromethyl)pyridine hydrochloride10 and
1,4-bis(sulfanylmethyl)benzene11 were prepared by literature
methods. The 1H and 13C NMR spectra were recorded on
a Gemini 200 spectrometer operating at 200 and 50 MHz
respectively, UV/vis/nir spectra on a Perkin-Elmer Lambda-9
UV/vis/nir spectrophotometer with a 60 mm MgO coated
integrating sphere diffuse reflectance attachment on samples
diluted with BaSO4 and infrared spectra on a Perkin-Elmer
Spectrum BX FT-IR System (samples in KBr disks). Elemental
analyses were performed by the Campbell Microanalytical
laboratory at the University of Otago.
its extensive interactions are largely responsible for the differ-
ence in the structure of 1 compared with 3 and 5. In contrast,
both copper polymers 3 and 5 have chelating polymeric links.
While the conformation of the ligands remains almost identical
[weighted RMS deviation: 0.275 Å] (Fig. 7a) in the two copper
polymers, the use of a longer CuI2Cu connector allows the
construction of a polymer with larger separation between
the linking ligands (Fig. 7b). The intra-chain para-ring
distance increases from 12.84 Å in 5 to 14.20 Å in 3. This results
in an offset of adjacent chains (Figs. 3 and 5) but the overall
orthogonal stacking of the sheets remains very similar. As a
result of this offset, the weak C(pyridine)–H ؒ ؒ ؒ para-ring
interactions which exist between adjacent chains of the same
layer in 5 are no longer present in 3 [C(pyridine)–H ؒ ؒ ؒ para-ring
4.61 Å]. Instead the small changes in chain positions
make C(methylene)–H ؒ ؒ ؒ pyridine interactions between ortho-
gonal chains in adjacent layers possible in 3 but not in 5
[C(methylene)–H ؒ ؒ ؒ pyridine 3.12 Å]. Despite these changes in
the CH/π interactions, which are the most significant inter-
molecular interactions between chains of the two copper
polymers, the overall packing does not alter dramatically. This
suggests that other weaker nondescript van der Waals inter-
actions rather than the easily identifiable CH/π interactions
may be important in controlling the overall packing. Indeed,
the surprising feature of the copper polymers is that despite the
Ligand preparation: 1,4-bis(2-pyridylmethylsulfanylmethyl)-
benzene (L)
2-Chloromethylpyridine hydrochloride (8.55 g, 0.0521 mol) in
EtOH (100 mL) was added, with stirring, to a solution of 1,4-
bis(sulfanylmethyl)benzene (4.44 g, 0.0261 mol) in CH2Cl2 (150
mL) and NaOH (8 g) in EtOH–water (80:20 v/v, 100 mL). The
reaction mixture was stirred for 24 h, filtered and reduced in
volume to give a brown residue which was dissolved in CH2Cl2
(50 mL). This solution was washed with water (2 × 50 mL),
dried (MgSO4) and concentrated to give crude product as a
brown solid. Recrystallisation from CH2Cl2–light petroleum
(bp 40–60 ЊC) gave pure L as fawn crystals (yield 5.80 g, 63.1%),
mp 75 ЊC (Found: C, 67.90; H, 5.85; N, 7.74; S, 18.37. Calc for
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Table 1 Crystallographic data for complexes 1, 3 and 5
1
3
5
Empirical formula
M
C10H14AgN2O5S
382.16
C10H10CuINS
366.71
C20H20Cl2CuN2S2
486.94
Crystal system
Space group
Triclinic
P1
Monoclinic
P21/n
Monoclinic
P21/n
¯
a/Å
b/Å
c/Å
α/Њ
5.187(2)
10.722(3)
12.636(4)
82.315(4)
78.712(4)
79.952(4)
674.9(3)
2
10.282(1)
9.793(1)
12.188(1)
8.017(2)
10.026(2)
13.063(3)
β/Њ
105.482(2)
90.816(3)
γ/Њ
U/Å3
1182.7(2)
4
1049.9(4)
2
Z
T/K
168(2)
1.665
158(2)
4.594
163(2)
1.501
µ/mmϪ1
Reflections collected
8633
2734 (0.0283)
0.0231
7964
4727
Unique reflections (Rint
R1 indices [I > 2σ(I)]
wR2 (all data)
)
2265 (0.0184)
0.0397
0.0906
2124 (0.0159)
0.0233
0.0651
0.0575
1
C10H10NS: C, 68.14; H, 5.72; N, 7.95; S, 18.19%). H NMR
(CDCl3): δ 8.55 [2H, d, 3J(HH) 4.9, H6Ј], 7.64 [2H, dt, 3J(HH)
7.7, 4J(HH) 1.8, H4Ј], 7.30 [2H, d, 3J(HH) 7.7, H3Ј], 7.25 (4H, s,
[Cu(L)Cl2]∞ 5. Crystallisation by slow diffusion of the two
reactants L and CuCl2 in MeOH consistently produced strongly
dichroic green/orange crystals that analysed as a 1:1 complex
(Found: C, 49.17; H, 4.40; N, 5.77. Calc. for C20H20Cl2CuN2S2:
C, 49.32; H, 4.14; N, 5.75%).
3
H2,3,5,6), 7.16 [2H, dd, J(HH) 4.9, 7.7 Hz, H5Ј], 3.76 (4H, s,
CH2) and 3.67 (4H, s, CH2). 13C NMR (CDCl3): δ 158.6, 149.3,
136.9, 136.8, 129.2 (C2,3,5,6), 123.2, 122.0, 37.6 and 35.7.
Bulk preparation. The reaction of ligand L (50 mg, 0.14
mmol) in MeOH (10 mL) with CuCl2 (19 mg, 0.14 mmol) in
MeOH (10 mL) immediately gave complex 5 as a light green
powder (yield 55 mg, 80%) (Found: C, 48.98; H, 4.32; N, 5.60;
S, 12.82. Calc. for C20H20Cl2CuN2S2: C, 49.32; H, 4.14; N, 5.75;
S, 13.17%). IR (KBr)/cmϪ1: 1598s, 1566m, 1510w, 1480s, 1431s,
1398m, 1314m, 841m, 769s, 710m, 676w and 523w. UV/vis/nir
(BaSO4)/cmϪ1: 4060m, 4110m, 4300m, 4350m, 4590w, 5080w,
5720w, 5960w, 9260s (br), 13 000s (br), 22 200 (sh), 26 300s and
33 300 (sh).
Complexes
[Ag2(L)(NO3)2ؒ4H2O]∞ 1. Reaction of ligand L (50 mg, 0.14
mmol) dissolved in MeOH (10 mL) with AgNO3 (48 mg, 0.28
mmol) dissolved in water (5 mL) immediately gave complex
1 as a white precipitate (yield 70 mg, 72%) (Found: C, 33.32;
H, 2.90; N, 7.77; S, 8.21. Calc. for C10H10AgN2SO3ؒH2O:
C, 33.00; H, 3.05; N, 7.69; S, 8.79%). IR (KBr)/cmϪ1: 1637m,
1594m, 1570w, 1514w, 1473m, 1384vs (br), 1301vs (br), 1156m,
853m, 753m, 706m, 670m and 520w. UV/vis/nir (BaSO4)/cmϪ1
4110m, 4350w, 4650w, 5100m, 5720w, 6000w, 6920w (br) and
39 200vs.
:
X-Ray crystallography
Diffraction data were collected on a Bruker SMART CCD
diffractometer with graphite monochromated Mo-Kα (λ =
0.71073 Å) radiation. Intensities were corrected for Lorentz-
polarisation effects22 and a multiscan absorption correction23
was applied. The structures were solved by direct methods
(SHELXS)24 and refined on F2 using all data by full-matrix
least-squares procedures (SHELXL 97).25 The hydrogen atoms
of the two water molecules of complex 1 were located by
Fourier difference and restrained to be 0.82 Å from the corre-
sponding oxygen atom. Detailed analyses of interactions within
the structures were carried out using PLATON26 or PARST.27
Crystallographic data for the three structures are listed in
Table 1.
[Cu2(L)Br2]∞ 2. Reaction of ligand L (50 mg, 0.14 mmol)
dissolved in MeCN (15 mL) with CuBr (41 mg, 0.28 mmol)
dissolved in MeCN (5 mL) immediately gave complex 2 as a
yellow powder (yield 70 mg, 77%) (Found: C, 37.83; H, 3.21; N,
4.57; S, 9.88. Calc. for C10H10BrCuN: C, 37.57; H, 3.15; N, 4.38;
S, 10.03%). IR (KBr)/cmϪ1: 1594s, 1566w, 1513w, 1476s, 1436s,
1391w, 1156w, 876w, 763s, 716m and 523w. UV/vis/nir (BaSO4)/
cmϪ1: 4060m, 4300m, 4390m, 4590w, 5090w, 5710w (br), 5980w,
25 400 (sh) and 37 900s.
[Cu2(L)I2]∞ 3. Reaction of ligand L (20 mg, 0.057 mmol) dis-
solved in MeCN (5 mL) with CuI (22 mg, 0.11 mmol) dissolved
in MeCN (5 mL) immediately gave the product as a yellow solid
(yield 40 mg, 95%) (Found: C, 32.84; H, 2.68; N, 3.79; S, 8.72.
Calc. for C10H10CuINS: C, 32.75; H, 2.75; N, 3.82; S, 8.74%).
IR (KBr)/cmϪ1: 1593s, 1567m, 1508m, 1472s, 1437s, 1399m,
1152m, 1013m, 852m, 766s, 751s, 711s, 686w, 512w and 416w.
CCDC reference number 186/1864.
See http://www.rsc.org/suppdata/dt/a9/a909601i/ for crystal-
lographic files in .cif format.
Acknowledgements
We thank Professor Ward T. Robinson and Dr Jan Wikaira
(University of Canterbury) for X-ray data collection and the
University of Otago for financial support.
UV/vis/nir (BaSO4)/cmϪ1
: 4050m, 4300m, 4340w, 4610w,
5090w, 5710w, 5980w, 26 000 (sh) and 36 400s.
[Cu2(L)Cl4]∞ 4. Reaction of ligand L (53 mg, 0.15 mmol) in
MeOH (10 mL) and CuCl2 (40 mg, 0.30 mmol) in MeOH
(10 mL) immediately precipitated complex 4 as a green solid
(yield 85 mg, 91%) (Found: C, 38.99; H, 3.37; N, 4.51; S, 10.66.
Calc. for C10H10Cl2CuNS: 38.66; H, 3.24; N, 4.51; S, 10.32%).
IR (KBr)/cmϪ1: 1602s, 1473m, 1438m, 1389m, 1163m, 1110w,
1018m, 850m, 787m, 770m, 713w and 526w. UV/vis/nir
(BaSO4)/cmϪ1: 4130m, 4380m, 4580w, 4650w, 5170w, 5800w,
6060w, 10 500s (br), 23 000s and 27 000s.
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