Anion-dependent coordinative networking of macrocycle with copper(i) halides

Article abstract of DOI:10.1039/c2ce25111f

An O₂S₂-macrocycle L incorporating three aromatic subunits was synthesized and structurally characterized by X-ray analysis. Four coordination polymers of L with copper(i) halides (Cl, Br and I) adopting different topologies and netw

Full text of DOI:10.1039/c2ce25111f

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PAPER
Anion-dependent coordinative networking of macrocycle with copper(I)
halides{
In-Hyeok Park,{ Hyun Jee Kim{ and Shim Sung Lee*
Received 24th January 2012, Accepted 19th April 2012
DOI: 10.1039/c2ce25111f
2 2
An O S -macrocycle L incorporating three aromatic subunits was synthesized and structurally
characterized by X-ray analysis. Four coordination polymers of L with copper(I) halides (Cl, Br and
I) adopting different topologies and network patterns depending on the anions are reported.
Reactions of L with copper(I) chloride and copper(I) bromide yielded a single-stranded one-
dimensional (1D) coordination polymer [CuCl (L)(CH CN)] (1) with an oxidized copper(II) centre
2
3
n
and a double-stranded 1D coordination polymer [(Cu
2
2 2 2 2 n
Br )(L) ]?4CH Cl ] (2), with each strand
linked by a rhomboid-type Cu Br unit. However, the reaction with copper(I) iodide under the same
2
2
conditions gave an emissive mixture of supramolecular isomers with an identical composition
[Cu (L) ]?CH Cl , adopting a regular (3a) and a tilted (3b) square-grid-type 2D coordination
polymers via cubane-type Cu I linking. The XRPD results also confirmed the binary mixture. The
{
4
I
4
2
2
2 n
}
4
4
conformational diversity in the ligand leads to a variation in overall structural motifs of the
supramolecular isomers.
Introduction
not only because of the variation of ligand rigidity but also
diverse bridging modes of the thiocyanate ion.
The sulfur-containing macrocycles, called thiacrowns or thiama-
crocycles, often form not only discrete type endocyclic meta-
llo-supramolecules but also infinite exo-coordination-based
networks in which some soft metal ions exist inside or outside
Among the soft metal salts employed in the above system,
copper(I) halides are particularly interesting because of their
(
n
CuX) -type cluster-based networking via its thiaphilic nature
7
associated with photoluminescence properties. The copper(I)
halides as a versatile member in coordination chemistry and
crystal engineering for noncyclic multidentate ligands are well
1
the macrocyclic cavity, respectively. In particular, the exocyclic
soft metal coordination networks with bridging coordinative
anions have been our interest because of their attractive high
2
dimensional structures and physical properties. Several cases of
8
documented and reviewed. In this case, however, a prediction of
the resulting structure still remains challenging. Furthermore, no
systematic structural work for the thiamacrocycles has been
reported so far for copper(I) coordination polymers with
the exo-coordination-based mono- and multinuclear complexes
of thiamacrocycles with an infinite form have been introduced by
2
us and others. We have also suggested that such endo- and exo-
3
9
different halide anions. So we have focused our attention on
coordination can be controlled by the choice of the anions with
4
different coordination abilities. Based on this behaviour, we
the halide anions which could potentially influence the resulting
8,10
products because of their different size, reactivity and so on.
2 2
have proposed an N-azo-coupled NS O -macrocycle system,
which illustrates how the coordinating ability of the anion
controls a colour change through formation of endo- or exo-
5
metal complexes. Very recently, we also reported the 1D and 2D
2 2
network coordination products of tribenzo-O S -macrocycle
isomers incorporating a xylyl group in the ortho-, meta- and
6
para- (L in this work) positions with mercury(II) thiocyanate. In
this case, all the polymeric products show different topologies
In connection with these reasons, we were motivated to
Department of Chemistry and Research Institute of Natural Science,
Gyeongsang National University, Jinju, 660-701, S. Korea.
E-mail: sslee@gnu.ac.kr
2 2
employ a tribenzo-O S -macrocycle L in which the two sulfur
donors are linked with the para-xylyl unit, giving inherent
macrocyclic ring rigidity and inducing the exo-coordination of
sulfur donors. A combination of the anion variation of the
copper(I) halides and the tendency for the exo-coordination of L
can serve as versatile controlling factors for the assembly of the
{
Electronic supplementary information (ESI) available: XRPD patterns
of 1 and 2, TGA of 1, 2 and 3, NMR spectra of L, EPR spectrum of 1.
CCDC reference numbers 863927–863931. For ESI and crystallographic
data in CIF or other electronic format see DOI: 10.1039/c2ce25111f/
{
These two authors contributed equally to this work.
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final structures of the respective polymeric networks, adopting
D and 2D features as depicted in Scheme 1. In particular, we
1
report the structural characteristics of two supramolecular
isomers of the copper(I) iodide coordination polymer, one of
which is a regular square-grid type isomer while the other adopts
a tilted square-grid analogue.
Results and discussion
Synthesis of ligand
Fig. 1 Crystal structure of L: (a) front view and (b) side view.
Synthesis of L began with salicylaldehyde (Scheme 2). The
dichloride precursor for the cyclisation was prepared through the
Preparation and structural description of 1D copper chloride and
bromide complexes (1 and 2)
1
dialdehyde and dialcohol. L was obtained by coupling reaction
1
between the dichloride precursor and 1,4-benzenedimethanethiol
The reaction of L with copper(I) chloride in an acetonitrile–
dichloromethane mixture resulted in an initial colourless reaction
mixture changing to green within 30 min at room temperature.
Slow evaporation of the green solution afforded a high yield
of a brown crystalline product 1 suitable for X-ray analysis. The
reaction solution and crystal colour together with its elemental
analysis initially suggested that it was a Cu(II) species and
subsequently confirmed by a crystal structure determination
in the presence of Cs
2 3
CO under high dilution condition in a
reasonable yield (65%).
L was also characterized in the solid state by single-crystal
X-ray crystallography. Colourless single crystals of L suitable for
X-ray analysis were obtained by slow evaporation of its
dichloromethane solution. The crystal structure is shown in
Fig. 1. As expected, the two sulfur donors are oriented in an
exodentate fashion while the two oxygen atoms are arranged
endodentate with respect to the ring cavity which adopts a nearly
(Fig. 2) and its EPR spectrum (Fig. S7{); selected geometric
parameters are presented in Table 1. The X-ray analysis
…
flat arrangement. The S S distance in the macrocycle is
˚
.166 A. The aliphatic ring segment corresponding to O1–C–
reveals that 1 features a 1D polymeric array of formula
7
2 3 n
[Cu(L)Cl (CH CN)] with an exo-coordination mode. The
C–C–O2 shows a gauche–anti arrangement in keeping with the
homogeneity of the product was confirmed by the XRPD
patterns (Fig. S1{). The framework shows a –L–Cu–L–Cu–
pattern and its asymmetric unit contains one L, one Cu atom,
two Cl atoms and one acetonitrile. The copper atom that lies
outside the cavity is five-coordinated and is bonded to two S
atoms from two adjacent L, two chloride ions and one
acetonitrile. The coordination geometry around the copper atom
can be described as a distorted trigonal bipyramid where Cl1,
Cl2 and N1 form the trigonal plane while S1 and S2A atoms
occupy the axial positions [/S1–Cu1–S2A 169.66(2)u].
more flexible nature than the restricted S2–C-Ar–C–S1 segment.
Slow diffusion of a dichloromethane solution of L into an
acetonitrile solution of copper(I) bromide afforded a pale yellow
crystalline complex 2. The complex 2 is a double-stranded 1D
2 2 2 2 2 n
polymer of formula {[(Cu Br )(L) ]?4CH Cl } (Fig. 3); selected
geometric parameters are presented in Table 2. The homogeneity
of the product was confirmed by the XRPD patterns (Fig. S2{).
The successive ligand molecules are linked with Cu-(m -Br) -Cu
2 2
rhomboid units via Cu–S bonds. The Cu(I) coordination sphere
is distorted tetrahedral, with the Cu-donor atom angles falling in
the range 103.09(2)–122.85(2)u. In 2, the intra- and interligand
Scheme 1 Structural diversity of copper halides complexes of L.
S
…
˚
S distances are 7.758 and 4.005 A, respectively. The Cu–S
˚
bond distances [2.269(1) and 2.292(1) A] agree well with the
1
2
˚
corresponding values [2.226–2.899 A] for related systems. Not
surprisingly given their hard nature, neither of the oxygen
donors of L participates in coordination. With respect to this
Scheme 2 Synthesis of L.
2 3 n
Fig. 2 Single-stranded 1D polymeric structure of 1, [Cu(L)Cl (CH CN)] .
4
590 | CrystEngComm, 2012, 14, 4589–4595
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a
˚
whose geometry resembles a distorted cube with alternating
vertices of Cu and I atoms is coordinated by four different
Table 1 Selected bond lengths [A] and bond angles [u] for 1
Cu1–S1
Cu1–N1
Cu1–Cl2
S1–Cu1–S2A
N1–Cu1–S2A
N1–Cu1–Cl2
Cl2–Cu1–S1
Cl2–Cu1–S2A
a
2.355(1)
2.191(2)
2.260(1)
169.66(2)
85.37(4)
Cu1–S2A
Cu1–Cl1
2.363(1)
2.266(1)
ligands via Cu–S bonds (Fig. 4b). In two isomers, the Cu I cores
4 4
show no major differences in their geometric parameters. Also
the Cu–S bond distances in both cases are quite similar. Each Cu
N1–Cu1–S1
N1–Cu1–Cl1
Cl1–Cu1–Cl2
Cl1–Cu1–S1
Cl1–Cu1–S2A
84.29(4)
111.73(5)
136.62(2)
96.678(18)
86.985(18)
atom is tetrahedrally coordinated to three m -I atoms and one S
3
111.73(5)
88.355(19)
95.633(19)
donor of L, with the ‘tetrahedral’ angles falling in the range
99.99(3)–114.03(3)u for 3a and 94.71(4)–119.85(4)u for 3b. The
larger dislocation from the regular tetrahedral angle for 3b
Symmetry codes: (A) x 2 1, y, z.
corresponds to its tilted conformation. Each L acts as a bis-
4 4
monodentate ligand and connects the two Cu I cores to form a
˚
[
(Cu
4
4
I )
˚
4
(L)
4
] unit with sides of 14.0 6 14.2 A in 3a and 13.5 6
˚
1
4.3 A in 3b and diagonal distances of 18.2 6 21.6 A in 3a and
7.1 6 21.8 A in 3b (Fig. 4c). The square-grid networks are not
˚
1
planar but undulating due to the tetrahedral geometry of the Cu
atoms. Because of the compact layer-to-layer packing of the
undulating square-grid sheet, the intersections of the grid in 3a
and 3b give almost no cavities (Fig. S8{). In both cases, one
dichloromethane molecule exists inside each unit.
To understand the conformational difference of the two
isomers, it is necessary to compare the conformation of L in 3a
and 3b. As already mentioned above, the para-xylyl unit in L has
an intrinsic rigidity but the dibenzo-ether unit is more flexible
Fig. 3 Double-stranded 1D polymeric structure of 2, {[(Cu
2 2 2
Br )(L) ]?
4
2
2 n
CH Cl } . The non-coordinating solvent molecules are omitted.
a
˚
Table 2 Selected bond lengths [A] and bond angles [u] for 2
because of the –O(CH
tion of L in each isomer is responsible for the torsion angles
between atoms in the –O(CH O– segment. Both of the two
2 3
) O– segment. Therefore, the conforma-
Cu1–S1
Cu1–Br1
Cu1–Cu1B
S1–Cu1–S2A
S2A–Cu1–Br1B
Br1–Cu1–S2A
a
2.269(1)
2.542(1)
2.927(1)
122.85(2)
105.94(2)
103.094(19)
Cu1–S2A
Cu1–Br1B
2.292(1)
2.472(1)
2 3
)
S1–Cu1–Br1B
S1–Cu1–Br1
Br1–Cu1–Br1B
111.43(2)
103.99(2)
108.577(13)
independent L molecules in 3a exhibit the gauche–anti con-
formation which means that the two ligands are similarly
somewhat twisted upon complexation. While the two indepen-
dent L molecules in 3b show different conformations, adopting
gauche–anti and anti–anti; the former is twisted and latter is quite
flat. All these data indicate the relative conformation of L which
is responsible for the discriminated square-grids 3a and 3b. In
other words, the conformational diversity in ligand L leads to a
variation in overall structural motifs.
Symmetry codes: (A) x, y + 1, z; (B) 2x, 2y + 1, 2z + 1.
2 2
pattern, similar copper(I) halide complexes of two O S -
1
3
macrocycles have been previously reported by us.
Preparation and structural description of 2D copper iodide
complexes (3a and 3b)
Solid-state photoluminescence studies were carried out at
room temperature (Fig. 6). Complexes 1 and 2 incorporating the
trigonal bipyramidal Cu(II) geometry and the rhomboidal
Slow diffusion of a dichloromethane solution of L into an
acetonitrile solution of copper(I) iodide yielded a pale yellow
crystalline product. X-ray analysis confirmed a mixture of two
supramolecular isomers with an identical chemical composition
2 2
Cu Br core, respectively, were found to be non-emissive. In
contrast, the compound 3a (with small amount of 3b), adopting
square-grid incorporating Cu4I4 cubane unit exhibits a broad
band with a bright green emission maximum at 537 nm, the latter
reflecting a cluster-centred (CC) excited state with mixed halide-
of {[Cu I (L) ]?CH Cl } ;
a
regular square-grid type 2D
coordination polymer (3a) and a tilted square-grid analogue
3b) (Fig. 4 and Fig. S8{). Selected geometric parameters are
4
4
2
2
2 n
1
4
(
to-metal charge transfer character (X/MLCT). In other words,
the photoluminescence of Cu (L) unit in 3a and 3b can come
presented in Tables 3 and 4. The comparison of the XRPD
results for the synthesized product with the simulated data for 3a
and 3b also confirmed that the product prepared is the binary
mixture (Fig. 5). Separation of the mixed products was not
possible but the expected content of 3b in the mixture is less than
4
X
4
4
from either the charge transfer from the halide-Cu metals to the
ligands (X/MLCT) or can arise from the d manifolds to an empty
7
,14
p orbital of the Cu
4
centre (CC).
Similar emission bands (530–
550 nm) originated from the Cu I cubane-type cluster have been
4
4
e,15
2
8
5
% as a minor product. To figure out the more stable phase in
also reported previously by us
and the D. Li group.
the mixed phases (3a and 3b), the XRD patterns at different
periods (fresh product and after eight months) were compared,
but no significant differences were observed.
As a comparative study, it is noteworthy that both the
copper(I) bromide and copper(I) iodide lead to the formation of
the anion-assisted networking, but they show different dimen-
sionalities and nuclearity. In formation of 3 (iodide), the cubane-
type Cu4I4 core with higher nuclearity probably induces the
higher dimensionality. In other words, the preferred 2D structure
of 3 with higher dimensionality and nuclearity could be
explained by the iodide ion being more reactive as a softer base
than the bromide ion which gives the 1D structure in 2. The
The crystal structures of 3a and 3b are similar except that 3a
has a rectangular unit whereas 3b possesses a rhomboidal one
due to its inclined structure. In fact, one side of the square-grid
network in 3b is tilted to 14u. In both cases, the asymmetric unit
contains two L molecules, one Cu4I4 cubane core and one
CH
2 2 4 4
Cl solvent molecule (Fig. 4a). Interestingly, the Cu I core
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Fig. 4 Comparison of the 2D network structures of (left) 3a, {[Cu
I
4 4
(L)
2
]?CH
2
Cl
2
}
n
and (right) 3b, {[Cu
I
4 4
(L)
2
]?CH
2
Cl
2
}
n
: (a) asymmetric units, (b)
basic coordination environments, (c) square-grid structures.
observed oxidation of copper(I) to copper(II) in the chloride
system for 1 can be considered because of the instability of CuCl
in solution and also can be, in part, explained due to the lower
reactivity of chloride ions compared to bromide and iodide ions
towards the copper(I) centre.
overall structural motifs of the supramolecular isomers.
Consequently, the driving forces of the complexations are
mainly based on the higher reactivity between soft acids
[copper(I)] and soft bases [sulfur and halides]. Since the order
2
2
2
of softness for the halides is I . Br . Cl , the softer anions
gave the more complex products with larger sizes or higher
dimensionalities.
Conclusions
Altering the copper(I) halide from chloride to iodide in
complexation with the thiaoxamacrocycle L causes a shift from
a 1D to a 2D anion-bridged framework. Copper(I) chloride
under the same reaction conditions results in a 1D framework
with an oxidized copper(II) centre and terminal chloride
coordination in terminal positions. In particular, the 2D product
derived from copper(I) iodide was revealed as an emissive
mixture of supramolecular isomers, adopting regular and tilted
square grids via cubane-type Cu4I4 linking. In this case, the
conformational diversity in the ligand leads to a variation in the
Experimental section
General procedures
All chemicals and solvents used in the syntheses were of reagent
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 Thermo Fisher Scientific
Nicolet iS 10 FT-IR spectrometer. The electrospray ionization
(ESI) mass spectra were obtained on a Thermo Scientific LCQ
Fleet spectrometer. The elemental analysis of L, 1, 2 and 3 were
4
592 | CrystEngComm, 2012, 14, 4589–4595
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a
˚
Table 3 Selected bond lengths [A] and bond angles [u] for 3a
Cu1–Cu2
Cu1–Cu4
Cu2–Cu3
Cu1–I1
Cu1–I2
Cu2–I1
Cu2–I3
Cu3–I4
Cu3–I3
Cu4–I1
Cu4–I3
I1–Cu1–I2
I2–Cu1–I4
I2–Cu2–S2
I2–Cu2–I3
I1–Cu2–I2
I4–Cu1–S1A
I2–Cu3–I4
I2–Cu3–S3
I4–Cu3–S3
I1–Cu4–I4
I3–Cu4–I4
I3–Cu4–S4B
a
2.727(1)
2.744(1)
2.707(1)
2.658(1)
2.667(1)
2.615(1)
2.666(1)
2.656(1)
2.667(1)
2.667(1)
2.707(1)
112.31(2)
112.28(2)
102.90(3)
111.86(2)
110.28(2)
102.81(3)
113.60(2)
99.99(3)
114.03(3)
113.886(19)
109.03(2)
103.19(3)
Cu1–Cu3
Cu2–Cu4
Cu3–Cu4
Cu1–I4
Cu1–S1A
Cu2–I2
Cu2–S2
Cu3–I2
Cu3–S3
Cu4–I4
Cu4–S4B
I1–Cu1–I4
I1–Cu1–S1A
I3–Cu2–S2
I1–Cu2–S2
I1–Cu2–I3
I2–Cu1–S1A
I3–Cu3–I4
I2–Cu3–I3
I3–Cu3–S3
I1–Cu4–I3
I1–Cu4–S4B
2.719(1)
2.691(1)
2.780(1)
2.713(1)
2.298(1)
2.774(1)
2.296(1)
2.683(1)
2.282(1)
2.620(1)
2.319(1)
111.16(2)
109.26(3)
102.37(3)
113.25(3)
115.30(2)
108.53(3)
109.14(2)
114.80(2)
104.79(3)
112.224(19)
102.67(4)
Fig. 5 Comparison of XRPD patterns: (top) as synthesized and
(
middle) 3a and (bottom) 3b simulated from the single crystal X-ray data.
Symmetry codes: (A) x, y 2 1, z; (B) x, 2y + 1, z + 1/2.
a
˚
Table 4 Selected bond lengths [A] and bond angles [u] for 3b
Cu1–Cu2
Cu1–Cu4
Cu3–Cu4
Cu1–I1
Cu1–I4
Cu2–I1
Cu2–I3
Cu3–I2
Cu3–I4
Cu4–I1
Cu4–I4
I1–Cu1–I2
I2–Cu1–I4
I1–Cu2–I3
I2–Cu3–I3
I3–Cu3–I4
I1–Cu4–I4
I1–Cu1–S1
I4–Cu1–S1
I4–Cu3–S3
I1–Cu2–S4B
I3–Cu2–S4B
I3–Cu4–S2B
a
2.770(9)
2.755(10)
2.662(9)
2.690(8)
2.697(8)
2.687(8)
2.679(8)
2.765(8)
2.672(8)
2.714(8)
2.657(8)
109.06(3)
116.79(3)
114.36(3)
111.96(3)
113.94(3)
111.98(3)
105.86(4)
107.04(4)
108.73(4)
106.74(4)
102.16(4)
102.74(4)
Cu1–Cu3
Cu2–Cu3
Cu2–Cu4
Cu1–I2
Cu1–S1
Cu2–I2
Cu2–S4A
Cu3–I3
Cu3–S3
2.654(1)
2.675(1)
2.747(1)
2.652(1)
2.321(2)
2.658(1)
2.295(2)
2.645(1)
2.277(1)
2.725(1)
2.303(2)
111.46(3)
108.99(3)
114.37(3)
113.85(3)
112.03(3)
111.82(3)
105.90(4)
112.07(4)
94.71(4)
109.70(4)
97.43(4)
119.85(4)
Cu4–I3
Fig. 6 Solid-state photoluminescence spectra of 1, 2 and 3a (with small
amount of 3b) at room temperature (excitation at 343 nm).
Cu4–S2B
I1–Cu1–I4
I1–Cu2–I2
I2–Cu2–I3
I2–Cu3–I4
I1–Cu4–I3
I3–Cu4–I4
I2–Cu1–S1
I3–Cu3–S3
I2–Cu3–S3
I2–Cu2–S4B
I1–Cu4–S2B
I4–Cu4–S2B
dichloromethane. Flash column chromatography on silica gel
using dichloromethane–n-hexane (v/v 3 : 7) gave L as a colour-
1
less solid. Yield: 65%; Mp: 158–159 uC. H NMR (300 MHz,
3
CDCl ): d 6.78–7.44 (m, 12H, Ar), 3.91 (t, 4H), 3.73 (s, 4H), 3.65
13
(
s, 4H), 1.96 (m, 2H). C NMR (75 MHz, CDCl ): d 156.51,
3
1
37.37, 130.82, 128.54, 126.52, 121.07, 112.4, 65.05, 35.49, 29.54.
IR (KBr disk): 2905, 2872, 1582, 1491, 1473, 1450, 1428, 1389,
1290, 1245, 1236, 1185, 1160, 1142, 1126, 1090, 1055, 1020, 953,
Symmetry codes: (A) 2x + 1, y + 1/2, 2z + 3/2; (B) 2x, y + 1/2, 2z + 3/2.
2
26, 749, 708, 686, 560, 456 cm . Anal. Calcd for [C25
1
8
26 2 2
H O S ]:
C, 71.05; H, 6.20; S, 15.18. Found: C, 71.31; H, 6.27; S, 15.16%.
+
carried out on a LECO CHNS-932 elemental analyzer after they
were dried in a vacuum at room temperature.
Mass spectrum: m/z = 423.08 [C25
27 2 2
H O S ] .
Preparation of [CuCl (L)(CH CN)] (1)
n
2
3
Synthetic details for L
Copper(I) chloride (11.7 mg, 0.118 mmol) in acetonitrile was
added to a solution of L (20.0 mg, 0.047 mmol) in dichlor-
omethane. The initial colourless reaction mixture changed to
green within 30 min at room temperature. Slow evaporation of
the green solution afforded a brown crystalline product 1
suitable for X-ray analysis. Yield: 20%. Mp: 172–173 uC
(decomp.). IR (KBr disk): 2923, 2858, 2362, 1646, 1598, 1491,
2 3
Cs CO (8.75 g, 26.9 mmol) was dissolved in DMF (500 mL) in a
flask and a syringe was filled with 1,3-bis(2-(chloromethyl)phe-
noxy)propane (4.16 g, 12.8 mmol) and 1,4-phenylenedimetha-
nethiol (2.17 g, 12.8 mmol) dissolved in DMF (30 mL). Under a
nitrogen atmosphere, the contents of the syringe was added at a
2
1
regular speed (0.6 mL h ) into the DMF solution maintaining
5–50 uC. 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
2
1
4
1457, 1413, 1286, 1250, 1101, 1040, 1017, 852, 751, 460 cm
.
H
29Cl
2
2 2
Anal. Calcd for [C27 CuNO S ]: C, 54.22; H, 4.89; N, 2.34;
(
S, 10.72. Found: C, 54.43; H, 4.81; N, 2.36; S, 10.63%.
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Table 5 Crystal and experimental data for L, 1, 2, 3a and 3b
L
1
2
3a
3b
Formula
T/K
Formula weight
Crystal system
Space group
C
173(2)
422.58
Orthorhombic
P2
25
H
26
O
2
S
2
C
173(2)
595.05
Monoclinic
P2 /c
27
H
26Cl
2
CuNO
2
S
2
C
173(2)
1471.76
Triclinic
54
H
60Br
2
Cl
8
Cu
2
O
4
S
4
C
173(2)
1691.84
Monoclinic
C2/c
51
H
54Cl
2
Cu
4
I
4
4
O S
4
51 2 4 4 4 4
C H54Cl Cu I O S
173(2)
1691.84
Monoclinic
P2 /c
¯
P1
1
2
1
2
1
1
1
˚
a/A
5.5135(2)
8.1356(3)
47.2858(14)
90
90
90
2121.03(13)
4
1.323
0.270
56.50
38 369
11.6776(6)
18.6014(10)
13.2518(7)
90
108.458(3)
90
2730.5(2)
4
1.448
1.174
56.00
49 050
11.2153(3)
11.6948(3)
12.9855(4)
85.0890(10)
65.1570(10)
79.3950(10)
1519.11(7)
2
1.609
2.548
52.00
24 176
36.215(4)
13.9659(14)
28.036(5)
90
125.048(4)
90
11 609(3)
8
1.936
3.850
54.00
51 195
17.0726(15)
21.8272(18)
16.3027(14)
90
110.571(4)u
90
5687.8(8)
4
1.976
3.929
56.00
53 038
˚
b/A
˚
c/A
a (u)
b (u)
c (u)
3
˚
V/A
Z
D
2
3
c
/g cm
2
1
m/mm
max (u)
Reflections collected
2
h
Independent reflections 5243 [R(int) = 0.0356] 6597 [R(int) = 0.1350] 5962 [R(int) = 0.0413] 12 638 [R(int) = 0.0587] 13 702 [R(int) = 0.1450]
1.155
2
Goodness-of-fit on F
1.055
0.0395, 0.1137
0.0368, 0.0918
1.062
0.0321, 0.0864
0.0348, 0.0885
1.073
0.0363, 0.0956
0.0414, 0.0992
1.025
0.0496, 0.1272
0.0675, 0.1403
R
R
1
, wR
, wR
2
2
[I . 2s(I)]
(all data)
0.0477, 0.1149
0.0490, 0.1157
1
Preparation of {[(Cu
Slow diffusion of a dichloromethane solution of L (20.0 mg,
.047 mmol) into an acetonitrile solution of copper(I) bromide
17.0 mg, 0.118 mmol) at room temperature afforded a pale
yellow crystalline complex 2. Yield: 60%. Mp: 199–200 uC
decomp.). IR (KBr disk): 2917, 2871, 1596, 1584, 1511, 1491,
2
Br
2
)(L)
2
]?4CH
2
Cl
2
}
n
(2)
in a riding manner along with the their respective parent atoms.
Relevant crystal data collection and refinement data for the
crystal structures of L, 1, 2, 3a and 3b are summarized in Table 5.
0
In the refinement procedure for L, the O1–CH
segment is disordered over two sites occupied in a 55 : 45 ratio
Fig. S9{).
2 2 2
–CH –CH –O2
(
(
(
1
1
468, 1453, 1428, 1416, 1400, 1386, 1287, 1239, 1192, 1164, 1152,
2
1
Acknowledgements
104, 1049, 1029, 951, 901, 757, 705, 673, 499 cm . Anal. Calcd
Cl Cu ]: C, 47.97; H, 4.34; S, 9.85. Found: C,
8.45; H, 3.82; S, 10.44%.
for [C52
H56Br
2
4
2 4 4
O S
This work was supported by World Class University (WCU)
project (R32-20003) and KRF (2011-0011064), Republic of
Korea.
4
Preparation of {[Cu
mixture)
4 4 2 2 2 n
I (L) ]?CH Cl } (3a and 3b as an isomeric
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