Syntheses, crystal structures and luminescent properties of three new halogencuprate(I) complexes with 4-(trimethylammonio)phenyldisulphide

Article abstract of DOI:10.1016/j.molstruc.2005.05.029

Reactions of CuX (X=I, Br) with TabHPF₆ (Tab=4- (trimethylammonio)benzenethiolate) under the existence of Et₃N or Et₄NI in open air gave rise to three novel halogencuprate(I) complexes with 4-(trimethylammonio)phenyldisulphide (Tab-Tab): [Tab-Tab][CuX₃] (1: X=I; 2: X=Br) and {[Tab-Tab][Cu₂I ₄]}_n (3). Compounds 1-3 are characterized by elemental analysis, IR spectra and X-ray crystallography. It was found that the Tab-Tab dication in 1-3 serves as a counterion to maintain the electrical neutrality of 1-3. The dianions of 1 and 2 have planar triangular geometry with each halide atom being bound to the central trigonally coordinated copper atom. The dianion structure of 3 has a unique one-dimensional wavy chain composed of butterfly shaped [Cu₂I₃] units linked by μ-I bridges. The luminescence properties of 1-3 along with [Tab-Tab]I₂ have also been investigated.

Full text of DOI:10.1016/j.molstruc.2005.05.029

Journal of Molecular Structure 784 (2006) 24–31
www.elsevier.com/locate/molstruc
Syntheses, crystal structures and luminescent properties of three new
halogencuprate(I) complexes with 4-(trimethylammonio)
phenyldisulphide
Jin-Xiang Chena, Yong Zhanga, Zhi-Gang Rena, Jian-Ping Langa,b,
*
aKey Laboratory of Organic Synthesis of Jiangsu Province, School of Chemistry and Chemical Engineering,
Suzhou University, 1 Shizi Street, Suzhou 215006, Jiangsu, P. R. China
bState Key Laboratory of Structural Chemistry of FJIRSM, Chinese Academy of Sciences, Fuzhou 350002, Fujian, P. R. China
Received 7 May 2005; accepted 20 May 2005
Available online 11 November 2005
Abstract
Reactions of CuX (XZI, Br) with TabHPF6 (TabZ4-(trimethylammonio)benzenethiolate) under the existence of Et3N or Et4NI in open
air gave rise to three novel halogencuprate(I) complexes with 4-(trimethylammonio)phenyldisulphide (Tab–Tab): [Tab–Tab][CuX3] (1: XZ
I; 2: XZBr) and {[Tab–Tab][Cu2I4]}n (3). Compounds 1–3 are characterized by elemental analysis, IR spectra and X-ray crystallography. It
was found that the Tab–Tab dication in 1–3 serves as a counterion to maintain the electrical neutrality of 1–3. The dianions of 1 and 2 have
planar triangular geometry with each halide atom being bound to the central trigonally coordinated copper atom. The dianion structure of 3
has a unique one-dimensional wavy chain composed of butterfly shaped [Cu2I3] units linked by m-I bridges. The luminescence properties of
1–3 along with [Tab–Tab]I2 have also been investigated.
q 2005 Elsevier B.V. All rights reserved.
Keywords: Synthesis; Crystal structure; Halogencuprate(I); 4-(Trimethylammonio)phenyldisulphide; Luminescence
1. Introduction
TabHPF6 (TabZ4-(trimethylammonio)benzenethiolate),
and so far several silver/Tab compounds have been isolated
and structurally determined [15,16]. However, when Hg(II)
salt was allowed to react with TabHPF6, no Hg/Tab
complex but a Hg(II) complexes with Tab–Tab dication
was isolated [12]. The resulting Tab–Tab dication in this
compound was probably derived from the oxidation of Tab
ligand by oxygen in open air. As an extension of this study,
we carried out the reactions of CuX (XZI, Br) with
TabHPF6, and three new halogencuprate complexes with the
Tab–Tab dication, [Tab–Tab][CuX3] (1: XZI; 2: XZBr)
and {[Tab–Tab][Cu2I4]}n (3), were obtained therefrom.
Herein we report their syntheses, crystal structures and
luminescent properties.
As in past decades, much interest in the recognition of the
disulphide continues to be motivated by its application as
potential ligand for metal ions in biological system [1–3].
The stability of the metal/disulphide complexes has been
studied and some of them are structurally determined [4–14].
These metal/disulphide complexes are often prepared
through the reactions of metal salts with neutral organic
disulphide [4–9]. However, only a few have been made from
metal salts with thiolates [10–14]. In these cases, the thiolates
used may be oxidized into cationic disulfides by various
oxidizing agents such as oxygen, nitric acid, hydrogen
peroxide, dimethyl sulfoxide and potassium ferricyanide.
On the other hand, we are interested in the preparation of
metal/thiolate complexes from the unique cationic thiol
2. Experimental
*
Correspondence author. Tel.: C86 512 65213506; fax: C86 512
65224783.
E-mail address: jplang@suda.edu.cn (J.-P. Lang).
2.1. General
TabHPF6 and [Tab–Tab]I2 were prepared according to
the literature method [17]. Other chemicals and reagents
0022-2860/$ - see front matter q 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2005.05.029

J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
25
were obtained from commercial sources and used as
received. All solvents were predried over activated
molecular sieves and refluxed over the appropriate drying
agents under argon. The IR spectra were recorded on a
Nicolet MagNa-IR 550 as KBr disk (4000–400 cmK1). The
elemental analyses for C, H, and N were performed on an
EA1110 CHNS elemental analyzer. The photoluminescent
spectra were performed on a Perkin–Elmer LS55
spectrofluorometer.
1485 (m), 1415 (w), 1126 (w), 1006 (w), 837 (s), 679
(w), 549 (m), 480 (w) cmK1
.
2.3. X-ray structure determination
All measurements were made on a Rigaku Mercury
CCD X-ray diffractometer by using graphite monochro-
˚
mated Mo Ka (lZ0.71070 A). Crystals of 1–3 suitable
for X-ray analysis were obtained directly from the above
preparations.
A yellow block crystal of 1 with
2.2. Syntheses
dimensions 0.45!0.40!0.10 mm, a yellow platelet of
2 with dimensions of 0.40!0.36!0.08 mm and a yellow
prism of 3 with dimensions of 0.35!0.20!0.15 mm
were mounted at the top of a glass fiber, and cooled at
193 K in a liquid nitrogen stream. Diffraction data were
collected at u mode with a detector-to-crystal distance of
34.63 mm (1), 34.52 mm (2) and 34.62 mm (3),
respectively. Cell parameters were refined by using the
program Crystalclear (Rigaku and MSc, Ver. 1.3, 2001)
on all observed reflections between q of 3.2 and 25.38 (1)
, 3.2 and 25.38 (2), 3.1 and 27.58 (3). A total of 720 (1,
2, 3) oscillation images were collected in the range 6.4!
2q!50.68 for 1, 6.4!2q!50.68 for 2 and 6.2!2q!558
for 3. The collected data were reduced by using the
program CrystalClear (Rigaku and MSC, Ver.1.3, 2001),
and an absorption correction (multiscan) was applied,
which resulted in transmission factors ranging from 0.110
to 0.617 for 1, from 0.09 to 0.597 for 2, and from 0.235
to 0.385 for 3. The reflection data were also corrected for
2.2.1. Synthesis of [Tab–Tab][CuI3] (1)
To a suspension containing TabHPF6 (125.2 mg,
0.4 mmol) in MeOH (5 ml) was added Et3N (0.25 ml).
The resulting colorless solution was then treated with a
solution of CuI (39 mg, 0.2 mmol) in MeCN (10 ml). The
mixture was stirred for 0.5 h and then filtered. Diethyl
ether (10 ml) was allowed to diffuse into the light yellow
filtrate. After standing it at ambient temperature for
several weeks, a large amount of insoluble gray materials
were precipitated coupled with yellow block crystals of
[Tab–Tab][CuI3] (1), which were separated by decanting
off the gray solids with large amount of MeOH/E2O
(v/vZ1 : 5), washed by Et2O and dried in vacuo. Yield:
19 mg (12% based on Cu). Anal. Calcd. for C18H26CuI3-
N2S2: C, 27.76; H, 3.37; N, 3.60. Found: C, 27.53; H,
3.20; N, 3.32. IR (KBr disc): 1621 (w), 1489 (m), 1416
(w), 1126 (w), 1009 (w), 837 (w), 680(w), 548 (m),
481(w) cmK1
.
Lorentz and polarization effects. The largest electron-
K3
density peak (1.314 e A ) in 1 was located 1.01(2) A
˚
˚
2.2.2. Synthesis of [Tab–Tab][CuBr3] (2)
from atom I(2) while that (1.450 e AK3) in 2 was 0.98
˚
The preceding method was employed with TabHPF6
(125.2 mg, 0.4 mmol), Et3N (0.25 ml), and CuBr (28.6 mg,
0.2 mmol) to form yellow platelets of [Tab–Tab][CuBr3] (2)
. Yield: 32.8 mg (35% based on Cu). Anal. calcd for
C18H26CuBr3N2S2: C, 22.97; H, 2.78; N, 2.98. Found: C,
22.78; H, 2.53; N, 2.79. IR (KBr disc): 1621 (w), 1489 (m),
1413(w), 1126 (w), 1009 (w), 837 (w), 680 (w), 548 (m),
˚
(1) A from atom Br(2).
The crystal structures of 1–3 was solved by direct
methods and refined on F2 by full-matrix least square
methods with SHELXTL-97 program [18]. All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were
located on their calculated positions and included in the
refinement of the structure factors. The final refinement
was based on 3815 (1), 2711 (2) and 5511 (3) reflections
with IO2.00s(I), and 242 (1), 242 (2) and 260 (3)
481 (w) cmK1
.
2.2.3. Synthesis of {[Tab–Tab][Cu2I4]}n (3)
2
variable parameters, and wZ1=½s2ðFo2ÞCð0:0567PÞ Š
To a solution containing CuI (78 mg, 0.4 mmol) in
MeCN (15 ml) was added Et4NI (102.6 mg, 0.4 mmol).
The resulting light yellow solution was treated with a
solution of TabHPF6 (125.0 mg, 0.4 mmol) in MeCN
(15 ml). The mixture was stirred for 1 h and filtered to
give a bright yellow solution. Diethyl ether (20 ml) was
allowed to diffuse into the filtrate. After standing it at
ambient temperature for about one week, yellow prisms
of {[Tab–Tab][Cu2I4]}n (3) were formed, which were
collected by filtration, washed by Et2O and dried in
vacuo. Yield: 180.3 mg (93% based on Cu). Anal. calcd
for C18H26Cu2I4N2S2: C, 22.30; H, 2.70; N, 2.89. Found:
C, 22.45; H, 3.02; N, 3.12. IR (KBr disc): 1623 (w),
2
(1),wZ1=½s2ðFo2ÞCð0:0600PÞ Š (2), wZ1=½s2ðFo2ÞC
2
ð0:0416PÞ C20:424PŠ (3) where PZðFo2 C2Fc2Þ=3. A
summary of the key crystallographic information for 1–3
is tabulated in Table 1. Crystallographic data for the
structural analysis have been deposited with Cambridge
Crystallographic Data Centre, CCDC reference numbers
251149 (1), 267597 (2) and 251150 (3). These data can
be obtained free of charge at www.ccdc.cam.ac.uk/
retrieving.html [or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
Fax: (internat.)C44 1223/336 033; E-mail: deposit@
ccdc.cam.ac.uk].

26
J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
Table 1
Crystallographic data for 1, 2 and 3
Compound
1
2
3
Molecular formula
Formula weight
Crystal system
Space group
C18H26CuI3N2S2
C18H26CuBr3N2S2
637.80
C18H26Cu2I4N2S2
969.25
778.80
Triclinic
PK1
Triclinic
PK1
Orthorhombic
Pbca
˚
a (A)
˚
b (A)
˚
c (A)
7.6778(6)
10.3539(9)
15.851(1)
84.740(5)
79.653(4)
84.621(4)
1230.5(2)
2
7.3652(6)
10.1272(9)
15.4426(14)
84.016(5)
81.344(5)
86.957(5)
1131.70(17)
2
19.8478(8)
10.4870(4)
25.7427(12)
84.016(5)
a (degrees)
b (degrees)
g (degrees)
3
˚
V (A )
Z
8
T/K
193
193
193
D
calc (g cmK3
)
2.102
1.872
2.403
˚
l(Mo-Ka) (A)
0.71070
48.27
0.71070
64.52
0.71070
63.61
m (cmK1
)
2qmax (degrees)
Total reflections
Unique reflections
No. of observations
No. of parameters
Ra
50.60
55.6
55.0
11953
11223
60622
4449 (RintZ0.042)
3815(IO2.00s(I))
242
4119(RintZ0.060)
2711(IO2.00s(I))
242
6133 (RintZ0.046)
5511(IO2.00s(I))
260
0.0396
0.0684
0.0412
wRb
0.0952
0.1609
0.0942
GOFc
˚
Drmax (e A
˚
Drmin (e A
0.0972
1.052
1.109
K3
)
1.314
1.450
0.825
K3
)
K1.332
K1.844
K0.819
P
RZ jjFojKjFcj=jFoj.
a
b
c
1=2
2
2
wRZfSwðFo2 KFc2Þ =SwðFo2Þ g
.
GOFZfS½wððFo2 KFc2Þ Þ=ðnKpÞg1=2, where nZnumber of reflections and pZtotal numbers of parameters refined.
2
3. Results and discussion
thiol TabHC was deprotonated by Et3N into a zwitterionic
species Tab, which may be further oxidized by O2 in air to
generate the Tab–Tab disulfide dication. In the latter
reaction (3), the proton of the thiol TabHC may be removed
during the oxidation of this thiol via O2 into the Tab–Tab
dication. In all three cases, the resulting Tab–Tab dication
acted as a counterion to stabilize the halogencuprate(I)
anions in solution, e.g. [CuX3]2K in 1 or 2 and [Cu2I4]2K in
3. Intriguingly, the formation of 1 or 2 was reproducible, but
was always accompanied with a large amount of gray
materials, which may be one main reason for the relatively
low yield for 1 or 2. Such gray solids were insoluble in
common organic solvents, which excluded their structural
characterization. Currently it is very difficult to explain the
formation of [CuX3]2K anions in 1 or 2.
3.1. Preparation and characterization of 1–3
Treatment of a suspension of TabHPF6 in MeOH with
excess Et3N afforded a colorless solution, to which was
added a solution containing 1/2 equivalent of CuI in MeCN.
The resulting yellow solution was stirred at room
temperature for 0.5 h and then filtered. Diffusion of Et2O
into the filtrate afforded yellow block crystals of [Tab–Tab]
[CuI3] (1) in 12% yield. The analogous bromide compound
[Tab–Tab][CuBr3] (2) was prepared as starting from CuBr
with 35% yield. On the other hand, reaction of CuI with
Et4NI in MeCN afforded a homogenous yellow solution,
which was treated with a solution of TabHPF6 in MeCN.
Similar workup to that used in the isolation of 1 or 2 led to
the formation of {[Tab–Tab][Cu2I4]}n (3) in 93% yield
(Scheme 1). In the former reactions (1 and 2), the cationic
Compounds 1–3 were relatively stable toward oxygen
and moisture. They were not soluble in common organic
solvents but soluble in water. The elemental analyses of 1–3
Scheme 1.

J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
27
Table 2
Selected bond distances (A) and angles (degrees) for 1, 2
˚
1
2
Cu(1)–I(1)
2.5091(7)
2.5465(7)
2.5355(7)
2.0538(17)
120.79(3)
122.09(3)
117.11(3)
Cu(1)–Br(1)
2.3771(15)
2.3736(15)
2.3498(14)
2.049(3)
Cu(1)–I(2)
Cu(1)–Br(2)
Cu(1)–I(3)
Cu(1)–Br(3)
S(1)–S(2)
S(1)–S(2)
I(1)–Cu(1)–I(3)
I(1)–Cu(1)–I(2)
I(3)–Cu(1)–I(2)
Br(3)–Cu(1)–Br(2)
Br(3)–Cu(1)–Br(1)
Br(2)–Cu(1)–Br(1)
118.16(6)
123.73(6)
118.09(6)
3.2. Crystal structures of 1 and 2
Having a common chemical formula [Tab–Tab][CuX3],
1 and 2 both crystallize in the triclinic space group PK1,
and the asymmetric unit contains one discrete Tab–Tab
dication and one [CuX3]2K dianion (1: XZI; 2: XZBr).
Their cell parameters are essentially identical, as are the
crystal structures. Therefore only the perspective view of 1
is shown in Fig. 1. Selected bond lengths and angles for 1
and 2 are compared in Table 2. The [CuX3]2K dianions in 1
and 2 are common, and can be found in several compounds
[19–23]. It has a planar triangular geometry with each halide
atom being bonded to the central trigonally coordinated
copper atom. This anion does not possess strict three-fold
symmetry in the solid state in that the Cu–X bond lengths
and X–Cu–X bond angles are not well equivalent. The mean
Fig. 1. The perspective view of the structure of 1.
were consistent with their chemical formula. In the IR
spectra of 1–3, characteristic bands due to vibrations of Ph
(1621, 1489, 1416 cmK1) and S–S bond (480–481 cmK1
were observed. The identities of 1–3 were finally confirmed
by X-ray crystallography.
)
˚
Cu–I bond length and I–Cu–I bond angle of 1 are 2.530(7) A
and 119.99(3)8, which are comparable to those observed in
Fig. 2. One-dimensional double-chain formed via the hydrogen bonding interactions in 1.

28
J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
Table 3
˚
Comparison on the S–S Bond Lengths (A) and CSSC torsion angle (degrees) in some disulphide compounds
Compounds
S–S Bond lengths
CSSC torsion angle
Ref.
a
{[C10H10N2S2][Cu2Cl6][BF4]2}n
[C12H26N2S2][CuCl4]b
2.032(1)
2.02(2)
81.5(2)
90.0(1)
74.83(1)
114.71(2)
86.3(2)
82.39(2)
82.1(4)
81.9(5)
80.4(4)
[4]
[10]
[{Me2NH(CH2)3S}2][CdBr4]
c
2.013(3)
2.049(3)
2.0628(5)
2.075(5)
2.0538(17)
2.049(3)
2.026(2)
[11]
[C10H22N2O4S2]Cl2
d
[24]
L–L$0.5C6H5CH3
e
[C8H22N2S2]Cl2
[25]
[26]
1
2
3
This work
This work
This work
a
C10H10N2S2Zbis(4-pyridinium)disulfide.
C12H26N2S2Zbis[4-N-methylpiperidinium]disulfide
[C10H22N2O4S2][Cl]2Z 3, 3, 30, 30-tetramethyl-D-cystin (D-penicillamine disulfide) dihydrochloride.
L–LZ2,20-bis[6-(2,20-bipyridyl)]diphenyldisulfide.
b
c
d
e
C8H22N2S2Zbis-[2-(N,N-dimethylamino)ethyl]disulfide dihydrochloride.
˚
[PPh3Me]2[CuI3] (2.554(3) A, 120.03(1))8 [19] and [Cp2-
˚
Co]2[CuI3] (2.545(2) A, 120.38(5))8 [21]. The mean Cu–Br
bond length and Br–Cu–Br bond angle of 2 are
˚
˚
(2.013(3) A) [11] and [C8H22N2S2]Cl2 (2.075(5) A;
C8H22N2S2Zbis-[2-(N,N-dimethylamino)ethyl]disulfide
dihydrochloride) [26]. The CSSC torsion angles of 1 and 2
are 82.1(4) and 81.9(5)8, respectively, which are compar-
able to that found in {[C10H10N2S2][Cu2Cl6][BF4]2}n
(81.5(2)8; C10H10N2S2Zbis(4-pyridinium)disulfide) [4],
but in-between those reported in [{Me2NH(CH2)3S}2]-
[CdBr4] (74.83(1)8) [11] and [C8H22N2S2]Cl2 (114.71(2)8;
C8H22N2S2Zbis-[2-(N,N-dimethylamino)ethyl]disulfide
dihydrochloride) [26].
˚
2.3668(14) A and 119.99(6)8, respectively, which are
˚
close to those reported in [PMe4]2[CuBr3] (2.365(3) A,
˚
120.00(1))8 [22] and [PPh3Me]2[CuBr3] (2.355(4) A,
Table 4
˚
Selected bond distances (A) and angles (degrees) for 3
Cu(1)/Cu(2)
Cu(1)–I(2)
2.6368(11)
2.6758(9)
2.7577(9)
2.5633(8)
2.026(2)
Cu(1)–I(1)
Cu(1)–I(3)
Cu(2)–I(2)
Cu(2)–I(4)
2.5417(8)
2.7366(9)
2.5422(9)
2.5232(8)
Having positive charges located on the NMe3 groups, the
Tab–Tab dications in the crystals of 1 and 2 are arranged
parallel to each other and the [CuX3]K dianions are
positioned among the dications. Such an arrangement
leads to interactions of halogen atoms with H atoms of the
methyl group of the Tab–Tab dication. The halogen atoms
are hydrogen-bond acceptor while H atoms of the methyl
are hydrogen-bond donor. As shown in Fig. 2, two hydrogen
bonding interactions between I(2) and the methyl group
Cu(1)–I(4B)
Cu(2)–I(3)
S(1)–S(2)
Cu(2)–I(2)–Cu(1)
Cu(2B)–I(4B)–Cu(1)
I(1)–Cu(1)–I(3)
I(1)–Cu(1)–I(4B)
I(3)–Cu(1)–I(4B)
I(4)–Cu(2)–I(3)
60.64(3)
Cu(2)–I(3)–Cu(1)
I(1)–Cu(1)–I(2)
I(2)–Cu(1)–I(3)
I(2)–Cu(1)–I(4B)
I(4)–Cu(2)–I(2)
I(2)–Cu(2)–I(3)
59.57(2)
116.64(3)
104.54(3)
106.53(3)
124.90(3)
113.95(3)
157.74(3)
114.71(3)
108.08(3)
105.54(3)
119.32(3)
˚
with C(18) [C(18)/I(2) (Kx, KyC1, KzC1) 3.07 A] and
between I(3) and the methyl group with C(9) [C(9)/I(3)
˚
(xK1, yK1, z) 3.07 A] led to the formation of a one-
dimensional zigzag chain extended along the c-axis. In
addition, the I(1) atom of the [CuI3]2K dianion has hydrogen
bonding interaction with the methyl group with C(7)
119.99(1))8 [23] (Table 2).
Table 3 lists comparison on the S–S bond lengths and
CSSC torsion angles of the disulfides in some known
complexes. The S(1)–S(2) bond lengths of 1 and 2 are
˚
2.0538(17) A and (2.049(3) A), respectively, which are
˚
similar to those reported in [C10H22N2O4S2]Cl2 (2.049(3) A;
˚
˚
[C(7)/I(1) (x–1, y, z) 3.09 A] in neighboring parallel
C10H22N2O4S2ZD-penicillamine disulfide dihydrochloride)
[24], and L–L$0.5C6H5CH3 (2.0628(5) A; L–LZ2,2 -bis[6-
(2,20-bipyridyl)]diphenyldisulfide) [25], but in-between
chain, thus forming a one-dimensional double-chain
structure. In the case of 2, however, only a one-dimensional
zigzag chain is stacked along c-axis by the hydrogen
bonding interactions between Br(1) and the methyl group
0
˚
those
observed
in
[{Me2NH(CH2)3S}2][CdBr4]
Fig. 3. One-dimensional chain formed via the hydrogen bonding interactions in 2.

J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
29
with C(18) [C(18)/Br(1) (KxC1, KyC1, KzC1)
˚
2.84 A] and between Br(2) and the methyl group with
˚
C(7) [C(7)/Br(2) (KxC2, KyC1, KzC2) 2.88 A]
(Fig. 3).
3.3. Molecular structure of 3
Compound 3 crystallizes in the orthorhombic space
group Pbca and the asymmetric unit contains one Tab–
Tab dication and one [Cu2I4]2K dianion. As shown in
Figs. 4–6, the I(4) atom serves a bridge to interconnect
[Cu2I3] fragments, forming an interesting 1D wavy chain
extended along the b-axis. The neighboring chains are
˚
9.47 A apart, and separated by Tab–Tab dications.
Although iodide-bridged copper(I) polymers are ubiqui-
tous in halogencuprate(I) complexes, those having a
wavy chain structure is uncommon. As shown in
Table 4, the Cu(2)–I(4)–Cu(1A) angle of 157.74(3)8 is
quite bent. The [Cu2I3 fragment consists of a butterfly
like [Cu(m-I)2Cu] fragment with a terminal I(1) atom
Fig. 4. The perspective view of the structure of 3.
Fig. 5. The perspective view of the neighboring chains containing hydrogen bonding interactions in 3.

30
J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
Fig. 6. The unit cell packing diagram of 3 looking down the b-axis.
coordinated to Cu(1). In this fragment, Cu(1) adopts a
distorted tetrahedral coordination geometry while Cu(2)
has a trigonal planar geometry. The Cu(1)/Cu(2)
separation (2.6368(11) A) within the [Cu(m-I)2Cu]
˚
rhomb is comparable to that in [CuIL]2 (2.609(2) A;
3.4. Luminecent properties of 1–3
Compounds 1, 2 and 3 exhibit luminescence in solid state
at ambient temperature as shown in Fig. 7. Their lifetimes
(11.32 ms (1), 11.46 ms (2) and 9.73 ms (3)) were measured
by time-resolved spectroscopy at room temperature and
calculated through the mono-exponential decay method. In
the emission spectra of 1–3, they have a broad band at ca.
566 nm (lexZ397), which is quite similar to that of the free
compound [Tab–Tab]I2 (lemZ566 nm, lexZ397). There-
fore, the possible origin of the emissions of 1–3 may be
˚
LZ1,10-phenanthroline) [27], but shorter than those
˚
observed in [CuIL]2 (2.803(2) A; LZ2,6-bis(3-pyridylox-
˚
y)pyrazine) [28] and [PPh4]2[Cu2I4] (2.957(1) A) [29].
The mean Cu-m-I bond length for trigonally coordinated
˚
Cu(2) is 2.542(8) A, which is similar to those of other
trigonally coordinated Cu complexes such as [PPh4]2[-
˚
˚
Cu2I4] (2.589(1) A) [29], [PPh3Me]2[Cu2I4] (2.572(2) A)
[30]. The average Cu-m-I bond distance for tetrahedrally
˚
coordinated Cu(1) is 2.7233(9) A, which is close to that
in other tetrahedrally coordinated Cu complexes such as
˚
[CuIL]2 (2.7297(9) A, LZ2,6-bis(3-pyridyloxy)pyrazine)
˚
[28], but longer than that of [PyH]2[Cu3I5] (2.6795(5) A)
˚
[31]. The terminal Cu(1)–I(1) distance (2.5417 (8) A) is
comparable to that of 1. The S–S bond length and CSSC
torsion angle in 3 are 2.026(2) and 80(4)8, respectively,
which are somewhat smaller than those of the
corresponding ones of 1 and 2.
As shown in Figs. 5 and 6, I(2) atom in the [Cu2I4]2K
dianion has H-bonding interaction with the methyl group
˚
of C(17) [C(17)/I(2) (Kx, yC3/2, KzC3/2) 2.90 A],
thus affording a one-dimensional chain with Tab–Tab
dications covering on its one side.
Fig. 7. The emission spectra of 1–3 and [Tab–Tab]I2 in the solid state at
ambient temperature.

J.-X. Chen et al. / Journal of Molecular Structure 784 (2006) 24–31
31
¨ ¨
[10] M.C. Brianso, J.L. Brianso, W. Gaete, J. Ros, Inorg. Chim. Acta. 49
attributable to the ligand-charge (LC) transition from S
(non-bonding 3p) to benzene ring (p*) or from benzene ring
(p*) to benzene ring (p*) of the Tab–Tab dication.
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[12] J.X. Chen, W.H. Zhang, Z.G. Ren, Y. Zhang, J.P. Lang, Acta
Crystallogr. E61 (2005) m60.
Acknowledgement
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J. Inorg. Chem. (2004) 4274.
The authors thank the National Natural Science
Foundation of China (No. 20271036), the NSF of Jiangsu
Province (No. BK2004205), State Key Laboratory of
Structural Chemistry of FJIRSM (No. 030066), and Key
Laboratory of Organic Synthesis of Jiangsu Province (No.
JSK001) for supporting this study.
[16] J.X. Chen, Q.F. Xu, Y. Zhang, Z.N. Chen, J.P. Lang, J. Organomet.
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