Synthesis, crystal structure, and characterization of a novel supramolecular cluster compound [(BPE)3(WOS3Cu 3Br4)2]

Article abstract of DOI:10.1080/15533174.2012.740743

Orange-yellow crystals of the title compound were obtained from the reaction of [NH₄]₂[WO₂S₂], CuI, and bpe·Br₂ (1:3:2) in DMF solution. And the crystal system is trigonal, space group P-3 c 1, with unit cell parameters a = 13.9730(15) A, b = 13.9730 A, c = 18.1365(19) A, and Z = 2. This cluster compound possesses a wheel-shaped supramolecular structure containing tetranuclear cluster core. Copyright Taylor & Francis Group, LLC.

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Synthesis, Crystal Structure, and Characterization
of a Novel Supramolecular Cluster Compound
[(BPE)3(WOS3Cu3Br4)2]
Ting Cao a , Hong Chen a , Chunguang Chen a , Yuqing Chen a , Zhenhua Zhang a & Yun-Yin
Niu a
a College of Chemical and Molecular Engineering , Zhengzhou University , Zhengzhou , P. R.
China
Accepted author version posted online: 04 Dec 2012.Published online: 26 Feb 2013.
To cite this article: Ting Cao , Hong Chen , Chunguang Chen , Yuqing Chen , Zhenhua Zhang & Yun-Yin Niu (2013) Synthesis,
Crystal Structure, and Characterization of a Novel Supramolecular Cluster Compound [(BPE)3(WOS3Cu3Br4)2], Synthesis and
Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:4, 417-419, DOI: 10.1080/15533174.2012.740743
To link to this article: http://dx.doi.org/10.1080/15533174.2012.740743
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:417–419, 2013
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.740743
Synthesis, Crystal Structure, and Characterization of a Novel
Supramolecular Cluster Compound [(BPE)3(WOS3Cu3Br4)2]
Ting Cao, Hong Chen, Chunguang Chen, Yuqing Chen, Zhenhua Zhang,
and Yun-Yin Niu
College of Chemical and Molecular Engineering, Zhengzhou University, Zhengzhou, P. R. China
EXPERIMENTAL
Orange-yellow crystals of the title compound were obtained
General Information and Materials
from the reaction of [NH4]2[WO2S2], CuI, and bpe·Br2 (1:3:2) in
The compound [NH4]2WS2O2[3] was prepared as described
DMF solution. And the crystal system is trigonal, space group P–3
c 1, with unit cell parameters a = 13.9730(15) Å, b = 13.9730 Å,
c = 18.1365(19) Å, and Z = 2. This cluster compound possesses
a wheel-shaped supramolecular structure containing tetranuclear
cluster core.
in the literature. The starting material bpe·2Br is described in
the Scheme 1. Other chemicals and solvents were obtained from
commercial sources and used as received without further purifi-
cation. Infrared spectra were recorded on a Shimadzu IR435
spectrometer (Japan) as KBr disk (4000–400 cm−1). Elemental
analyses (C, H, and N) were carried out on a FLASH EA 1112
elemental analyzer (Italy).
Supplemental materials are available for this article. Go to the
publisher’s online edition of Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry to view the supplemen-
tal file.
Keywords cluster compound, crystal structure, template effect
Synthesis of the Organic Cation BPE
10 mmol 1,2-dibromoethane was added into a round flask
(100 mL), then added the solution into 60 mL pyridine and
stirring the solution for 10 h at the temperature of 100◦C. After
cooling and filtering, the crystals of the complex were obtained
by the method of recrystallization in the solvent of methanol and
ethyl ether. The yield of this cation reached 90%. The synthesis
method was conducted in the following reaction (Scheme 1).
INTRODUCTION
Since the fact that Fe-S-Mo compounds are synthetic models
of the catalytic site of the enzyme nitrogenase is discovered,
cluster compounds have been a research focus owning to their
unique features, such as good catalytic effect, powerful magnetic
and electric performance, high biological activity, and so on.[1,2]
Pyridine and its derivatives are very common and impor-
tant heterocyclic groups among the variety of organic ligands
with azotic heterocyclic ring, which can interact with most of
the transition metal ions. Therefore, the study of the unique
cluster compound becomes a main interest of our group. In re-
cent experiment, the title compound [(BPE)3(WOS3Cu3Br4)2]
SCH. 1. The preparation of dication pyridinium bpe·2Br.
For the synthesis of the cluster compound
[(BPE)3(WOS3Cu3Br4)2] (5), put [NH4]2[WO2S2] 0.114 g
(5 mmol), CuI 0.285 g (15 mmol), and bpe·2Br 0.334 g
(10 mmol) into an agate mortar, after grinding adequately,
30 mL DMF was added. Transfer the solution into a 100 mL
round flask. Refluxed and stirred the solution in the oil bath
at 85◦C for about 10 h. After this, filtering the solution until
an orange red solution was obtained. Then putting it in a dark
place, orange red crystals were obtained after a week with
about 46% yield. Anal. Calcd for C36H42Br8Cu6N6O2S6W2: C,
19.90; H, 1.93; N, 3.87; Found (%): C, 19.95; H, 1.96; N, 3.55.
IR (KBr, cm−1): 3449.05s, 1660.21s, 1601.26s, 1487.23m,
1411.25s, 915.37m, 802.13s, 679.78m, 429.85m.
(BPE
=
(C12H14N2)2+
) was prepared by reaction of
[NH4]2[WO2S2] with bpe·Br2 (BPE = (C12H14N2)2+) in DMF.
In the present article we report the synthesis and crystal structure
of this cluster compound.
Received 15 February 2012; accepted 13 October 2012.
The authors acknowledge the NSFC (No. 21171148, J1103309).
Address correspondence to Yun-Yin Niu, College of Chemical and
Molecular Engineering, Zhengzhou University, Zhengzhou 450052,
P. R. China. E-mail: niuyy@zzu.edu.cn
417

418
T. CAO ET AL.
TABLE 1
Selected crystal structure data for compound
CCDC No.
868495
Empirical formula
Formula weight
Temperature [K]
Crystal system
Space group
Crystal sizes [mm]
a [Å]
C36H42Br8Cu6N6O2S6W2
2171.34
100(2)
Trigonal
P–3 c 1
0.15 × 0.15 × 0.02
13.9730(15)
13.9730
18.1365(19)
90
b [Å]
c [Å]
α [o]
β [o]
90
120.00
3066.6(5)
2
γ [o]
V [Å3]
Z
F(000)
2028
2.351
11.224
ρ [g cm−3
]
μ [mm−1
]
FIG. 1. The basic structure unit of the compound.
data/restrains/parameters
1805/0/100
1.092
0.0725
0.1661
3.506/–2.135
GOF on F2
unit, are connected with a μ3-bridging bromine atom and form
a complete cubane structure. In the structure, all the coordina-
tion modes of the three copper are the same and it is distorted
tetrahedron. Every copper is connected with two sulfur atoms,
a terminal bromine atom, and a μ3-bridging bromine atom and
then forms a cluster anion [WOS3Cu3] (Figure 1). The bond
length of Cu1-Br1 and Cu1-Br2 is 2.824(2) and 2.4151(19) Å,
respectively. Organic cations are freely surrounding cluster an-
ion unit. From the packing figure of the compound (Figure 2),
we can see that every cubane cluster anion is surrounded by six
cations and cluster anions are filled in the caves of the cations.
What’s interesting is that the supramolecular structure is similar
to a wheel as a whole if we see it from the c-axis.
a
R1 = [I > 2σ (I)]
wR2 (all data)
ꢀρmax/ꢀρmax (e Å−3
)
aR1 = ꢀFo| – |Fcꢀ/ |Fo|; wR2) [w(Fo2 – Fc2)2/ w(Fo2)2]1/2
.
RESULTS AND DISCUSSION
Crystal Structure of the Compound
[(BPE)3(WOS3Cu3Br4)2]
Its formula is [(C12H14N2)3(WOS3Cu3Br4)2]. The crystal
structure (Figure 1, Table 1) is composed of organic cation
BPE and cluster anion [WOS3Cu3Br4]3−, in which they are
connected through electrostatic interaction. The bond lengths
and bond angles of the title compound are accordingly listed in
Table 2.
Preparation and the Template Effect
In this work, we selected 1,2-bis(pyridinium)ethane cation
Crystal structure analysis revealed that the oxidation states of because we found that they possessed ideal size and adjustabil-
W and Cu are +6 and +1, respectively. The three copper atoms, ity for structure directing. In order to explore the template effect
which are in the distorted cubane of the [WOS3Cu3] cluster of this quaternary ammonium cation on the heterothiometallitic
TABLE 2
The main bond lengths and bond angles of the compound
W(1)-O(1)
1.683(16)
W(1)-S(1)
2.256(3)
W(1)-Cu(1)
Br(2)-Cu(1)
S(1)-W(1)-S(1)
Cu(1)-Br(1)-Cu(1)
Br(2)-Cu(1)-Br(1)
2.692 (2)
2.415 (2)
108.24 (9)
71.66 (7)
101.38 (7)
Br(1)-Cu(1)
Cu(1)-S(1)
O(1)-W(1)-S(1)
O(1)-W(1)-Cu(1)
Cu(1)-W(1)-Cu(1)
2.824 (2)
2.296 (4)
110.68 (8)
134.85 (4)
75.76 (6)
Symmetry codes: #1 –x + y + 1, –x + 1, z #2 –y + 1, x – y, z #3 y, x, –z + 1/2.

A NOVEL SUPRAMOLECULAR CLUSTER COMPOUND
419
Cambridge, CB2 1EZ, UK (fax: 44-1223-336-033; email: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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compounds, we adopted a similar synthesis method. In fact,
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formed directly from the reaction of [MOS3]2−, copper salts,
and the template. However, compared to the preparation of
(NH4)2MOS3, the starting reagent (NH4)2MS2O2 exhibited
in higher yield, stability, and simpler synthetic procedure.[3]
In addition, according to the previous works, in the assem-
bly process, [MS2O2]2− could be transformed to [MS3O]2− [4]
.
Advisedly, we chose (NH4)2(MS2O2) (M = Mo, W) instead
of (NH4)2(MS3O) as the starting reagents for the assembly
of title heterothiometallic [Mo/WOS3Cu3]-based polymer. The
compound was synthesized at low heating temperatures. To
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SUPPLEMENTARY MATERIALS
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Center,
CCDC No. 868495. Copies of this information may be ob-
tained free of charge from The Director, CCDC, 12 Union Road,