Synthesis, crystal structures and calculated nonlinear optical properties of seven di-nuclear metal (0, I) carbonyl cyclohexanthiolates, [M2(μ-SC6H11)x(CO)y]n- (M = Mo, W; x = 2, 3; y = 6, 8; n = 0, 1, 2)

Article abstract of DOI:10.1016/j.jorganchem.2006.11.027

Seven novel di-nuclear molybdenum and tungsten metal cluster complexes with cyclohexanthiolate ligand, [Et₄N]₂[Mo₂(SC₆H₁₁)₂(CO)₈] (1), [Et₄N][Mo₂(SC₆H₁₁)₃(CO)₆] (2), [Ph₄P][Mo₂(SC₆H₁₁)₃(CO)₆] (3), [(CH₃)₃PhCH₂N][Mo₂(SC₆H₁₁)₃(CO)₆] (4), [Et₄N]₂[W₂(SC₆H₁₁)₂(CO)₈] (5), [W₂(SC₆H₁₁)₂(CO)₈] (6) and [Et₄N][W₂(SC₆H₁₁)₃(CO)₆] (7) have been synthesized and characterized. The crystal structure determinations reveal that 1 and 5 contain a planar [M(0)₂S₂] unit, 6 contains a planar [M(I)₂S₂] unit and 2, 3, 4 and 7 contain a [M(I)₂S₃] core with a planar M₂S₂ unit coordinated by a third chair form SC₆H₁₁ bridging ligand (M = Mo, W). IR of these seven complexes was measured. Theory calculation indicated that compounds 2 and 7 possess large first-order hyperpolarizability of 13 × 10^-30 esu and 8 × 10^-30 esu, respectively, which could be an IR second-order nonlinear optical candidate materials.

Full text of DOI:10.1016/j.jorganchem.2006.11.027

Journal of Organometallic Chemistry 692 (2007) 1411–1420
www.elsevier.com/locate/jorganchem
Synthesis, crystal structures and calculated nonlinear
optical properties of seven di-nuclear metal (0,I) carbonyl
cyclohexanthiolates, [M2(l-SC6H11)x(CO)y]nꢀ
(M = Mo,W; x = 2,3; y = 6,8; n = 0,1,2)
*
Zhangfeng Zhou, Botao Zhuang , Kechen Wu, Ping Liu, Yongqin Wei, Yuangen Yao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research On The Structure Of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian 350002, China
Received 17 October 2006; received in revised form 17 November 2006; accepted 17 November 2006
Available online 29 November 2006
Abstract
Seven novel di-nuclear molybdenum and tungsten metal cluster complexes with cyclohexanthiolate ligand, [Et4N]2[Mo2(SC6H11)2
(CO)8] (1), [Et4N][Mo2(SC6H11)3(CO)6] (2), [Ph4P][Mo2(SC6H11)3(CO)6] (3), [(CH3)3PhCH2N][Mo2(SC6H11)3(CO)6] (4), [Et4N]2[W2
(SC6H11)2(CO)8] (5), [W2(SC6H11)2(CO)8] (6) and [Et4N][W2(SC6H11)3(CO)6] (7) have been synthesized and characterized. The crystal
structure determinations reveal that 1 and 5 contain a planar [M(0)2S2] unit, 6 contains a planar [M(I)2S2] unit and 2, 3, 4 and 7 contain
a [M(I)2S3] core with a planar M2S2 unit coordinated by a third chair form SC6H11 bridging ligand (M = Mo,W). IR of these seven
complexes was measured. Theory calculation indicated that compounds 2 and 7 possess large first-order hyperpolarizability of
13 · 10ꢀ30 esu and 8 · 10ꢀ30 esu, respectively, which could be an IR second-order nonlinear optical candidate materials.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: M (Mo,W)2S2,3 unit; De-carbonylation; Crystal structures; Nonlinear optical property
1. Introduction
owing to the potential device applications in IR spectro-
scopic region [3]. Recently, transition-metal sulfur clusters
have grown into a new promising class of NLO material
[4], and have gradually been paid attention to by virtue
of their possessing the combined advantages of both
organic polymers and inorganic semiconductors [5,6]. The
multinuclear molybdenum and tungsten complexes are
one of the systems that having been investigated [7]. The
binuclear molybdenum carbonyl complexes containing
thiolate bridges, with a planar [Mo2S2] core were synthe-
sized in 1984 by reaction of Mo(CO)6 with thiolate
ligands[8]. These metal–carbonyl complexes undergo
reversible two-electron oxidation accompanied by metal–
metal bond formation [9,10]. Decarbonylation of [M2
(l-SR)2(CO)8]2ꢀ,0 and the subsequent reaction of its core
[M2S2] (M = Mo,W) are attractive because it may be
used to further synthesize a variety of multinuclear metal
With the development of laser technique, optical com-
munication, optical signal processing and transmission,
optical data acquisition and storage, optical computing,
optical electronic modulation, and especially optical limit-
ing effects utilized in the protection of optical sensors, tre-
mendous interest has been aroused to search for new
nonlinear optical (NLO) materials, so the design and syn-
thesis of new NLO materials become the subject of the cur-
rent research interest, and represent a new active research
field [1,2]. And transition-metal cluster nonlinear optical
(NLO) materials have attracted increasing interest recently
*
Corresponding author. Tel.: +86 591 83792426; fax: +86 591
83714946.
E-mail address: zbt@fjirsm.ac.cn (B. Zhuang).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.11.027

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Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
complexes. In order to discuss the influence of R ligand on
the [M2S2]-core in these compounds, and the difference
between Mo analog and W analog with cyclohexanthiolate
ligand, in this paper we report the synthesis, structure,
spectroscopic characterization and primary theoretical cal-
culation of seven new metal thiolate carbonyl compounds
by introducing a new chair-form C6H11S-ligand which is
different from aryl and alky to M2S2 unit: [Et4N]2[Mo2
(SC6H11)2(CO)8] (1), [Et4N][Mo2(SC6H11)3(CO)6] (2), [Ph4P]
[Mo2(SC6H11)3(CO)6] (3), [(CH3)3PhCH2N] [Mo2(SC6H11)3
(CO)6] (4), [Et4N]2[W2(SC6H11)2(CO)8] (5), [W2(SC6H11)2
(CO)8] (6) and [Et4N][W2(SC6H11)3(CO)6] (7). The struc-
ture determinations indicate that there are three modes
of structure in these complexes. (i) M2(0)–S2 core without
M. . .M bonding (in 1 and 5) (A); (ii) M2(I)–S2 core with
M–M bonding (in 6) (B) and (iii) M2(I)–S3 core with
M–M bonding (in 2, 3, 4 and 7) (C). Two of the seven
compounds have been theoretically predicted to have con-
siderable molecular NLO activity. And, furthermore,
these two compounds are non-centrosymmetric, so, they
may be promising second-order nonlinear optical materi-
als which can be applied in IR region.
Mo(CO)6 reacts with C6H11SNa in the presence of Et4NCl
at 50 ꢁC affording [Et4N]2[Mo2(SC6H11)2(CO)8] (1) (Reac-
tion 1), 1 undergoes oxidation by I2 to give [Mo2(SC6H11)2
(CO)8] (10) and [Mo2(SC6H11)2(CO)6(CH3CN)2] (100) when
toluene and MeCN were used as solvent (Reactions 2
and 3), respectively [11,12]. 10 or 100 reacts with C6H11SNa
in the presence of Et4NCl resulting in [Et4N][Mo2(SC6
H11)3(CO)6] (2) (Reactions 4 and 5). Interestingly and
unexpectedly, both reaction of Mo(CO)6 with C6H11SNa
in the presence of Et4NCl at 85 ꢁC for 24 h and the solution
of 1 in MeCN standing in refrigerator at 4 ꢁC for 3 months
can afford compound 2 also (Reactions 6 and 7). It is obvi-
ous that reactions 6 and 7 involve with an oxidation of Mo
atom, although not any oxidant have been added in these
two reactions. The oxidation may be attributed to a small
amount of air, which remains in the Schlenk tube because
the degassing is not thorough. The remainder air is too less
to influence the synthetic reaction at room temperature and
in short reaction time, but the remainder air may become
an oxidant at high temperature and even at low tempera-
ture in long reaction time. So, the reaction 6 should
contain formation of [Mo2(SC6H11)2(CO)8]2ꢀ (Reaction
a), oxidation of [Mo2(SC6H11)2(CO)8]2ꢀ by O2 (Reaction
b) and substitution of MeCN in Mo2(SC6H11)2(CO)6
(CH3CN)2 by SC6Hꢀ11 (Reaction c), and the real reaction
7 should involve oxidation of [Mo2(SC6H11)2(CO)8]2ꢀ
(Reaction a), decomposition of [Mo2(SC6H11)2(CO)8]2ꢀ
to generate ligand SC6Hꢀ11 (Reaction d) and substitution
of MeCN in Mo2(SC6H11)2(CO)6(CH3CN)2 by SC6H1ꢀ1
(Reaction c)
2-
0
1-
S
S
S
S
S
S
M
M
M
M
M
M
S
A
B
C
2. Results and discussion
85ꢁC
2ꢀ
MoðCOÞ6 þ SC6Hꢀ11
½Mo ðSC H Þ ðCOÞ ꢂ
ðaÞ
ðbÞ
ꢀꢀ!
2
6
11
2
8
MeCN
2.1. Synthesis and synthetic reaction of compounds 1–7
2ꢀ
½Mo2ðSC6H11Þ2ðCOÞ8ꢂ
O2
The synthesis and synthetic reaction for compounds 1–7
is described in Schemes 1 and 2. As is shown in Scheme 1,
Mo ðSC H Þ ðCOÞ ðCH CNÞ
ꢀꢀ!
2
6
11
3
2
6
2
MeCN
C6H11SNa
˚C
4˚C for 3 months
[
(CH3)3PhCH2N]
[
(CH3)3PhCH2N]
2
[Mo2(SC6H11)3(CO)6]
[Mo2(SC6H11)2(CO)8]
(CH3)3PhCH2NBr
4
C6H11SNa
Reaction 6
O2
85˚C
Mo(CO)6
Reaction 1
[Mo2(SC6H11)2(CO)6(CH3CN)2]
1''
Reaction 3
Reaction 5
C6H11SNa
Et4NCl
C6H11SNa
Et4NCl
50˚C
MeCN
Reaction 7
I2
4
˚C for 3 months
[Et4N[Mo2(SC6H11)3(CO)6]
2
[Et4N]2[Mo2(SC6H11)2(CO)8]
1
Reaction 8
air
MeCN
Reaction 2
Reaction 4
Et4NCl C6H11SNa
[Mo2(SC6H11)2(CO)8]
1'
Toluent
I2
Reaction 9
[PPh4][Mo2(SC6H11)3(CO)6]
3
CH3(CH2)2COONa
Ph4PBr
Scheme 1.

Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
1413
4oC for 3 months
85oC
Et4NCl
[Et4N]2[W2(SC6H11)2(CO)8]
W(CO)6
NaSC6H11
5
toluent
I2
85oC
Et4NCl
[W2(SC6H11)2(CO)8]
6
[Et4N][W2(SC6H11)3(CO)6]
7
NaSC6H11
Scheme 2.
Mo2ðSC6H11Þ2ðCOÞ6ðCH3CNÞ2 þ SC6H1ꢀ1
! ½Mo2ðSC6H11Þ ðCOÞ ꢂꢀ þ MeCN
of molybdenum analogs. The only difference is: high tem-
perature is required for reaction of W-analog.
ðcÞ
3
6
dec
2ꢀ
½Mo2ðSC6H11Þ2ðCOÞ8ꢂ ! SC6Hꢀ11 þ Mo ꢀ SC6H1ꢀ1 ꢀ CO ðdÞ
2.2. Molecular structures of compounds 1–7
As a matter of fact, compound 1 in MeCN underwent oxi-
dation to give compound 2 in about 4 weeks at room tem-
perature when a certain amount of air was injected in the
Schlenk tube (Reaction 8). The phenomenon of air infiltra-
tion leading to the valence enhancement of Mo atom has
been reported in our previous paper [13,14]. Compound
4, [(CH3)3PhCH2N] [Mo2(SC6H11)3(CO)6], can be synthe-
sized according to Reaction 1 and Reaction 7 by using
(CH3)3PhCH2NBr instead of Et4NCl.
It is worth pointing out that compound 3, [Ph4P]-
[Mo2(SC6H11)3(CO)6] was obtained from the reaction of
[Mo2(SC6H11)2(CO)8] with Ph4PBr and CH3CH2CH2-
COONa at 50 ꢁC in 24h (Reaction 9). This implies that
the presence of CH3CH2CH2COONa may accelerate the
decomposition of [Mo2(SC6H11)2(CO)8] to generate
SC6Hꢀ11 and the SC6H1ꢀ1 is more easy to react with
[Mo2(SC6H11)2(CO)8] giving [Mo2(l-SC6H11)3(CO)6]ꢀ
than CH3CH2CH2COOꢀ giving [Mo2(l-SC6H11)2(l-CH3-
CH2CH2COO)(CO)6]ꢀ.
The structures of the anion of 1, 2, 5 and 7 are shown in
Figs. 1–3 and 5, respectively. The molecular structure of 6
is depicted in Fig. 4. Selected bond lengths and angles are
listed in Table 1–7, respectively.
Compound 1 consists of three discrete structural
fragments, two Et4N+ cations and an di-anion [Mo2
(SC6H11)2(CO)8]2ꢀ. As is shown in Fig. 1 and Table 1,
the [Mo2(SC6H11)2(CO)8]2ꢀ is centrosymmetric and is com-
prised of two equivalent Mo atoms, each of which bonds to
four terminal carbonyls and two bridging chair-form
SC6H11 ligands in trans-arrangement on the different sides
of the [Mo2S2] plane, the geometry of each molybdenum
(0) atom is a distorted octahedron with two coordinated
sulfur atoms and four coordinated carbon atoms and a
small SMoS angle of 81.69ꢁ. The large Moꢃ ꢃ ꢃMo distance
˚
of 3.94 A implies non-bonding of metalꢃ ꢃ ꢃmetal which
meets the requirement of an 18-electron configuration of
each Mo atom for stabilization. The bimetal core unit
As is shown in Scheme 2, the synthesis and synthetic
reaction of tungsten analogs 5, 6 and 7 are similar to those
C23
C33
O4
C4
C34
C30
C24
C22
C35
O4
O1
O3
C3
C21
C32
C25
Mo2
O5
C5
C4
Mo1
C1
C20
C14
O2
C15
C31
C2
O6
C6
O3
C3
S1
S4
S3
C10
Mo1
C2
O2
C1
O1
C13
S5
C12
C10
C11
C15
C14
C13
C11
C12
Fig. 1. The structure of the anion of compound 1 with displacement
ellipsoids drawn at the 30% probability level. H atoms have been omitted
for clarity.
Fig. 2. The structure of the anion of compound 2 with displacement
ellipsoids drawn at the 30% probability level. H atoms have been omitted
for clarity.

1414
Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
C53
C55
C51
C14
C44
C43
C54
O21
C21
C13
C15
C16
O13
C42
C41
C52
C12
C45
C56
C13
C22
C11
W2
O22
C22
O23
C12
C46
S3
C23
O22
O24
O21
S1
S2
C24
C21
C11
W1
O11
W1
C31
O12
S1
C23
C32
O23
C33
C36
C35
C34
Fig. 5. The structure of the anion of compound 7 with displacement
ellipsoids drawn at the 30% probability level. H atoms have been omitted
for clarity.
Fig. 3. The structure of the anion of compound 5 with displacement
ellipsoids drawn at the 30% probability level. H atoms have been omitted
for clarity.
molybdenum (I) atom is distorted octahedron with three
coordinated sulfur atoms and three coordinated carbon
atoms. The bond angle of Mo–S–Mo is 70.81ꢁand the
MoS2Mo is a plane with a Mo–S bond distance of
2.6063 A.
˚
˚
Mo–Mo distance is 2.8562(7) A indicating an interaction
Compound 2 consists of two discrete structure frag-
ments, an Et4N+ cation and an anion [Mo2(SC6H11)3
(CO)6]ꢀ. As is shown in Fig. 2 and Table 2, the
[Mo2(SC6H11)3(CO)6]ꢀ has a [Mo2S3] core with a planar
Mo2S2 unit and is comprised of two equivalent Mo+ atoms
each of which bonds to three terminal carbonyls and three
bridging chair-form SC6H11 ligands two of them are
located on the same side of the planar Mo2S2-unit in cis-
arrangement and the third one is on the other side with a
longer Mo–S bond length. The anion of 2, [Mo2(SC6H11)3
(CO)6]ꢀ, is centrosymmetric and the geometry of each
between two metal atoms.
Compounds 3 and 4 are similar to compound 2 except
their cations, [Ph4P]+ (for 3) and [(CH3)3PhCH2N]+ (for
4). The anion of 3 and 4 are the same as that of 2.
Table 1
˚
Selected bond lengths (A) and bond angles (ꢁ) for [Et4N]2[Mo2(SC6H11)2-
(CO)8] (1)
Mo(1)–C(1)
Mo(1)–C(4)
Mo(1)–C(2)
S(1)–Mo(1)–S(10)
1.943(3)
1.957(3)
2.007(3)
81.69(2)
Mo(1)–C(3)
2.033(3)
2.6039(7)
2.6087(7)
98.31(2)
Mo(1)–S(1)
Mo(1)–S(10)
Mo(1)–S(1)–Mo(10)
O4
C16
C15
C4
C17
O1
Table 2
˚
C1
W1
Selected bond lengths (A) and bond angles (ꢁ) for [Et4N][Mo2(SC6H11)3-
(CO)6] (2)
O3
C3
C2
O2
Mo(1)–C(1)
Mo(1)–C(3)
Mo(1)–S(4)
Mo(1)–S(5)
1.933(8)
1.982(10)
2.482(2)
2.6096(18)
2.8562(7)
1.919(8)
1.987(9)
77.57(6)
73.66(7)
54.45(5)
54.52(5)
56.12(4)
74.41(6)
54.43(4)
Mo(1)–C(2)
Mo(1)–S(3)
Mo(2)–C(5)
Mo(2)–S(3)
Mo(2)–S(4)
Mo(2)–S(5)
S(3)–Mo(1)–S(4)
S(4)–Mo(2)–Mo(1)
S(5)–Mo(2)–Mo(1)
Mo(1)–S(3)–Mo(2)
Mo(2)–S(4)–Mo(1)
Mo(2)–S(5)–Mo(1)
S(3)–Mo(2)–S(4)
S(3)–Mo(2)–S(5)
2.006(8)
2.455(2)
2.017(9)
2.456(2)
2.468(2)
2.5801(19)
C14
O6
C18
S1
C6
C19
C25
S2
O7
C24
C23
Mo(1)–Mo(2)
Mo(2)–C(6)
Mo(2)–C(4)
S(3)–Mo(1)–S(5)
S(4)–Mo(1)–S(5)
S(3)–Mo(1)–Mo(2)
S(4)–Mo(1)–Mo(2)
S(5)–Mo(1)–Mo(2)
S(4)–Mo(2)–S(5)
S(3)–Mo(2)–Mo(1)
C20
C21
107.97(6)
C8
W2
C7
54.99(5)
57.10(4)
71.12(6)
70.49(6)
66.78(4)
108.40(7)
78.12(6)
O8
C5
O5
C22
Fig. 4. The structure of the compound 6 with displacement ellipsoids
drawn at the 30% probability level. H atoms have been omitted for clarity.

Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
1415
Table 3
Table 7
˚
˚
Selected bond lengths (A) and bond angles (ꢁ) for [Ph4P][Mo2(SC6H11)3-
(CO)6] (3)
Selected bond lengths (A) and bond angles (ꢁ) for [Et4N][W2(SC6H11)3-
(CO)6] (7)
Mo(1)–C(3)
Mo(1)–C(2)
Mo(1)–C(1)
Mo(1)–S(2)
Mo(1)–S(1)
Mo(1)–S(3)
Mo(1)–Mo(2)
S(2)–Mo(1)–Mo(2)
S(1)–Mo(1)–Mo(2)
S(3)–Mo(1)–Mo(2)
S(2)–Mo(2)–S(1)
S(2)–Mo(2)–S(3)
S(1)–Mo(2)–S(3)
S(2)–Mo(2)–Mo(1)
1.933(6)
2.004(5)
2.021(5)
2.4558(13) Mo(2)–S(2)
2.4593(16) Mo(2)–S(1)
Mo(2)–C(4)
Mo(2)–C(5)
Mo(2)–C(6)
1.935(6)
2.003(5)
2.014(5)
2.4689(14)
2.4741(14)
2.5623(18)
54.20(4)
56.78(4)
71.27(4)
108.78(4)
77.05(5)
70.95(6)
71.12(4)
67.58(4)
W(1)–C(13)
W(1)–C(12)
W(1)–C(11)
W(1)–S(3)
W(1)–S(2)
W(1)–S(1)
W(1)–W(2)
S(3)–W(1)–S(2)
S(3)–W(1)–S(1)
S(2)–W(1)–S(1)
S(3)–W(1)–W(2)
S(2)–W(1)–W(2)
S(1)–W(1)–W(2)
S(3)–W(2)–S(2)
1.932(15)
2.021(14)
2.015(16)
2.459(3)
2.474(3)
2.583(4)
2.8614(8)
107.72(12)
77.50(11)
73.45(11)
54.24(8)
W(2)–C(21)
W(2)–C(22)
W(2)–C(23)
W(2)–S(3)
W(2)–S(2)
W(2)–S(1)
S(3)–W(2)–S(1)
S(2)–W(2)–S(1)
S(3)–W(2)–W(1)
S(2)–W(2)–W(1)
S(1)–W(2)–W(1)
W(2)–S(3)–W(1)
W(2)–S(2)–W(1)
W(2)–S(1)–W(1)
1.949(15)
1.946(19)
1.975(15)
2.452(3)
2.464(4)
2.577(3)
77.74(11)
73.72(11)
54.48(8)
54.76(8)
56.41(9)
71.27(9)
70.82(9)
67.36(8)
2.596(2)
Mo(2)–S(3)
2.8691(10) S(1)–Mo(2)–Mo(1)
54.58(3)
54.68(3)
55.64(4)
107.89(5)
77.47(5)
71.30(6)
54.15(3)
S(3)–Mo(2)–Mo(1)
Mo(1)–S(2)–Mo(2)
S(2)–Mo(1)–S(1)
S(2)–Mo(1)–S(3)
S(1)–Mo(1)–S(3)
Mo(1)–S(1)–Mo(2)
Mo(2)–S(3)–Mo(1)
54.42(9)
56.22(8)
108.29(13)
Compound 5 consists of three discrete structural frag-
ments, two Et4N+ cations and an anion [W2(SC6H11)2
(CO)8]2ꢀ which is comprised of 2 equiv. W atoms, each
bonds to four terminal carbonyls and two bridging chair-
form SC6H11 ligands in trans-arrangement on the different
sides of the [W2S2] plane. As is shown in Fig. 3 and Table 5,
the anion of 5, [W2(SC6H11)2(CO)8]2ꢀ, is centrosymmetric
and the geometry of each tungsten(0) atom is distorted
octahedron with two coordinated sulfur atoms and four
coordinated carbon atoms. The S–W–S bond angle is
Table 4
˚
Selected bond lengths (A) and angles (ꢁ) for [(CH3)3PhCH2N][Mo2-
(SC6H11)3(CO)6] (4)
Mo(1)–C(1)
Mo(1)–C(3)
Mo(1)–C(2)
Mo(1)–S(2)
Mo(1)–S(1)
Mo(1)–S(3)
Mo(2)–S(1)
S(2)–Mo(1)–S(1)
S(2)–Mo(1)–S(3)
S(1)–Mo(1)–S(3)
S(2)–Mo(1)–Mo(2)
S(1)–Mo(1)–Mo(2)
S(3)–Mo(1)–Mo(2)
Mo(1)–S(2)–Mo(2)
1.85(2)
2.04(2)
2.09(2)
Mo(2)–S(3)
Mo(1)–Mo(2)
Mo(2)–C(4)
Mo(2)–C(6)
Mo(2)–C(5)
Mo(2)–S(2)
S(2)–Mo(2)–S(1)
S(2)–Mo(2)–S(3)
S(1)–Mo(2)–S(3)
S(2)–Mo(2)–Mo(1)
S(1)–Mo(2)–Mo(1)
S(3)–Mo(2)–Mo(1)
Mo(1)–S(1)–Mo(2)
Mo(2)–S(3)–Mo(1)
2.573(5)
2.8818(10)
1.86(2)
1.93(3)
1.99(2)
2.431(5)
2.440(5)
2.598(5)
2.465(5)
107.41(16)
78.48(16)
72.27(16)
54.04(11)
54.43(12)
55.72(11)
72.42(14)
2.447(5)
106.12(16)
78.69(15)
72.30(16)
53.54(11)
53.61(12)
56.55(11)
71.97(15)
67.72(11)
˚
80.81ꢁ. The large Wꢃ ꢃ ꢃW distance of 3.956 A implies non-
bonding of metalꢃ ꢃ ꢃmetal which meets the requirement of
an 18-electron configuration of each W atom for stabiliza-
tion. The bimetal core unit WS2W is a plane with a W–S
˚
bond distance of 2.598 A. The axial W–C distance
˚
˚
(2.001 A) is longer than the equatorial one (1.937 A), so
the C–O distance of the equatorial carbonyl is obviously
different from that of the axial carbonyl. This is obviously
due to the opposite effect.
Table 5
˚
Compound 6 is centrosymmetric, the geometry around
each W atom is a distorted octahedron with two S atoms
from bridging chair-form SC6H11 ligands and four carbon
atoms from carbonyls. As is shown in Fig. 4 and Table 6,
Selected bond lengths (A) and bond angles (ꢁ) for [Et4N]2[W2(SC6H11)2-
(CO)8] (5)
W(1)–C(21)
W(1)–C(24)
W(1)–C(23)
W(1)–C(22)
W(10)–S(1)–W(1)
1.955(13)
1.919(12)
1.985(13)
2.016(15)
99.19(9)
W(1)–S(1)
2.596(3)
2.599(3)
2.599(3)
80.81(9)
S(1)–W(10)
W(1)–S(10)
˚
˚
the distance of W–S and bond angle of W–S–W are 2.483 A
S(10)–W(1)–S(1)
and 73.75ꢁ, respectively. The W–W distance is 2.9762 A
indicating an interaction between two metal atoms. Like
the compound 5, the four carbonyls coordinated to each
tungsten atom are unequal in the W–C bond distances.
˚
The axial W–C distance (2.042 A) is longer than the equa-
Table 6
˚
˚
torial one (2.012 A), so the C–O distance of the equatorial
Selected bond lengths (A) and bond angles (ꢁ) for [W2(SC6H11)2(CO)8] (6)
carbonyl is obviously different from that of the axial car-
W(1)–C(4)
W(1)–C(1)
W(1)–C(3)
W(1)–C(2)
W(1)–S(2)
W(1)–S(1)
W(1)–W(2)
S(2)–W(1)–S(1)
S(2)–W(1)–W(2)
S(1)–W(1)–W(2)
W(2)–S(2)–W(1)
2.01(2)
2.014(17)
2.040(19)
2.044(17)
2.481(4)
W(2)–C(8)
W(2)–C(5)
W(2)–C(6)
W(2)–C(7)
W(2)–S(2)
W(2)–S(1)
S(2)–W(2)–W(1)
S(2)–W(2)–S(1)
S(1)–W(2)–W(1)
W(2)–S(1)–W(1)
1.986(17)
2.001(15)
2.03(2)
2.055(17)
2.477(4)
2.478(4)
53.17(9)
106.41(13)
53.24(9)
73.71(12)
˚
bonyl, also the average W–C distance (2.027 A) of com-
˚
pound 6 is longer than that of the compound 5 (1.969 A).
This implies that the donation of electrons of W to carbo-
nyls for compound 6 is more than that for compound 5.
Compound 7 consists of two discrete structure frag-
ments, an cation, Et4N+, and an anion [W2(SC6H11)3
(CO)6]ꢀ which has a [W2S3] core containing a planar
2.484(4)
2.9762(9)
106.09(13)
53.05(9)
53.05(9)
73.79(12)
˚
W2S2 unit with W–S of 2.467 A and is comprised of
2 equiv. W+ atoms, each of which bonds to three terminal

1416
Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
carbonyls and three bridging chair-form SC6H11 ligands.
As is shown in Fig. 5 and Table 7, two of the SC6H1ꢀ1
ligands are located on the same side of the planar W2S2-
unit in cis-arrangement and the third one is on the other
sensitive to air. Their color turned green from yellow
quickly if exposed in air for a while. This is the reason
why the compound [Et4N][M2(SC6H11)3(CO)6] could be
obtained easily without additional oxidant, but [Et4N]-
[M2(SPh)3(CO)6] could not.
˚
side with a longer W–S bond length of 2.583 A. The anion
of 7, [W2(SC6H11)3(CO)6]ꢀ, is centrosymmetric and the
geometry of each tungsten (I) atom is distorted octahedron
with three coordinated sulfur atoms and three coordinated
carbon atoms. The bond angle of W–S–W is 69.82ꢁ, and
In Table 8, it also can be found that the W–W, W–S, W–
C distances and W–S–W angles of the W2S2 core for W(I)
compounds [W2(SC6H11)2(CO)8], [W2(SPh)2(CO)8][19],
[W2(S-t-Bu)2(CO)8] [20] and [W2(SMe)2(CO)8] [21] are
comparable although compound 6 contains SC6Hꢀ11 ligand.
The Mo analog compounds have the same phenomenon.
So we may come to a conclusion that introduction of
C6H11 group has much more influence to M(0)–S2–M(0)
core than to M(I)–S2–M(I) core. Also, inspecting 2, 7 and
Ph-ligand containing-compound [Et4N][Mo2(SPh)3(CO)6]
[19], it is found that Mo–S distance of the Mo(I)–S2–
Mo(I) core for these three compounds are comparable,
while the Mo–Mo distances and Mo–S–Mo angles of 2
and 7 are smaller than those of [Et4N][Mo2(SPh)3(CO)6],
this may attribute to the larger stereo hindrance of the
chair-form C6H11 ligand than Ph ligand.
˚
the W–W distance of 2.8614 A indicates an interaction
between two metal atoms.
Comparison of l-C6H11 ligand containing-Mo(0), W(0)
compounds 1 and 5 with Ph and alkyl ligands containing
compounds [Et4N]2[Mo2(SPh)2(CO)8][10], [Et4N]2[Mo2
(SC6H13)2(CO)8][15], [Et4N]2[W2(SPh)2(CO)8][16] and
[Et4N]2[W2(SEtO2CH3)2(CO)8][17] (Table 8). It can be
found that M–C and M–S distances of the M2S2 (M =
Mo, W) core for all those complexes are comparable. While
the M–S–M angles of 1 (98.31ꢁ) and 5 (99.19ꢁ) with C6H11-
ligand are smaller than that of [Et4N]2[Mo2(SC6H13)2
(CO)8] (99.72ꢁ), [Et4N]2[W2(SEtO2CH3)2 (CO)8] (100.3ꢁ)
[Et4N]2[Mo2(SPh)2 (CO)8] (102.55ꢁ) and [Et4N]2[W2(SPh)2
(CO)8](103.10ꢁ). In terms of the results derived from a the-
oretical study [18], the electronic structure for d6–d6 com-
plexes, [M2(CO)8(l-SR)2]2ꢀ(M = Mo,W), is p*2d*2r2d2
p2r*2 and the occupied p* and r* levels, especially the r*
level, rise sharply with a decrease of the M–S–M bridging
angle. So the smaller M–S–M angle leads to the rise of
the occupied r* level and thus the electrons filled in the
r* orbital become more unstable and can be taken out eas-
ily resulting in the two-electron oxidation of the M(0)
dimer to the M(I) dimer accompanied by formation of
the M–M bond in order to satisfy the 18-electron configu-
ration around each d5 M atom if certain conditions such as
the presence of oxidant (I2 for example) or electrolysis are
provided. The fact that the M–S–M angles of compounds 1
and 5 with C6H11-ligand are smaller than that of the ana-
logs with phenyl and other alkyl ligands implies that com-
pounds 1 and 5 are easier to be oxidized than the analogs
with Ph and other alkyl ligands. In fact, 1 and 5 are very
2.3. IR spectra
IR data of compounds 1, 5, [Et4N]2[Mo2(SPh)2(CO)8],
[Et4N]2[W2(SPh)2(CO)8],
[Et4N]2[Mo2(SC6H13)2(CO)8]
and [Et4N]2[W2(SEtO2CH3)2(CO)8] are listed in Table 9.
Obviously, only four absorptions in 1727–2073 cmꢀ1 which
are assigned to tco could be observed in compounds
[Et4N]2[Mo2(SPh)2(CO)8] and [Et4N]2[W2(SPh)2(CO)8]
and 6–8 absorptions could be found in [Et4N]2[Mo2
(SC6H13)2(CO)8], [Et4N]2[W2(SEtO2CH3)2(CO)8], com-
pound 1 and compound 5. This shows that the character
of chair-form C6H11-ligand is more similar to alkyl ligand
than to Ph ligand.
2.4. Theory calculation of compounds 2 and 7
The ab initio study on the first hyperpolarizability of 2
(Fig. 6 shows the molecular model and its orientation)
Table 8
˚
Selected bond distances (A) and bond angles (ꢁ) of [Et4N]2[Mo2(SC6H11)2(CO)8] (1), [Et4N]2[Mo2(SPh)2(CO)8], [Et4N]2[Mo2(SC6H13)2(CO)8], [Et4N]2[W2-
(SC6H11)2(CO)8] (5), [Et4N]2[W2(SPh)2(CO)8], [Et4N]2[W2(SEtO2CH3)2(CO)8], [W2(SC6H11)2(CO)8] (6), [W2(SPh)2(CO)8], [W2(S-t-Bu)2(CO)8],
[W2(SMe)2(CO)8], [Et4N][Mo2(SC6H11)3(CO)6] (2), [Et4N][W2(SC6H11)3(CO)6] (7), [Et4N][Mo2(SPh)3(CO)6]
Compound
M–M
M–S
M–S–M
M–C
M–S0
M–S0–M
Ref.
[Et4N]2[Mo2(SC6H11)2(CO)8] (1)
[Et4N]2[Mo2(SPh)2(CO)8]
[Et4N]2[Mo2(SC6H13)2(CO)8]
[Et4N]2[W2(SC6H11)2(CO)8] (5)
[Et4N]2[W2(SPh)2(CO)8]
[Et4N]2[W2(SEtO2CH3)2(CO)8]
[W2(SC6H11)2(CO)8] (6)
[W2(SPh)2(CO)8]
[W2(S-t-Bu)2(CO)8]
[W2(SMe)2(CO)8]
[Et4N][Mo2(SC6H11)3(CO)6] (2)
[Et4N][W2(SC6H11)3(CO)6] (7)
[Et4N][Mo2(SPh)3(CO)6]
3.944
4.069
3.979
3.955
4.056
3.962
2.976
2.969
2.988
2.970
2.856
2.861
2.877
2.6063
2.608
2.6023
2.598
2.591
2.580
2.483
2.477
2.477
2.473
2.469
2.467
2.468
98.31
102.55
99.72
99.19
103.10
100.33
73.75
73.66
74.20
73.79
70.81
71.05
71.32
1.985
1.985
1.985
1.969
1.981
1.985
2.023
2.028
2.028
2.014
1.974
1.973
1.95
This work
[10]
[15]
This work
[16]
[17]
This work
[19]
[20]
[21]
2.610
2.583
2.585
66.78
67.36
67.65
This work
This work
[19]

Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
1417
Table 9
IR data for [Et4N]2[Mo2(SC6H11)2(CO)8] (1), [Et4N]2[Mo2(SPh)2(CO)8], [Et4N]2[Mo2(SC6H13)2(CO)8] and [Et4N]2[W2(SC6H11)2(CO)8] (5), [Et4N]2-
[W2(SPh)2(CO)8], [Et4N]2[W2(SEtO2CH3)2(CO)8]
Compounds
t(co) (cmꢀ1
)
Ref.
[Et4N]2[Mo2(SC6H11)2(CO)8] (1)
[Et4N]2[Mo2(SPh)2(CO)8]
1755, 1813, 1882, 1946, 1996, 2029, 2040, 2073
1770, 1840, 1900, 2000
This work
[10]
[Et4N]2[Mo2(SC6H13)2(CO)8]
[Et4N]2[W2(SC6H11)2(CO)8] (5)
[Et4N]2[W2(SPh)2(CO)8]
1738, 1770, 1835, 1870, 1940, 1980
1755, 1811, 1874, 1936, 1973, 1986, 2025, 2038
1794, 1839, 1886, 1988
[15]
This work
[16]
[Et4N]2[W2(SEtO2CH3)2(CO)8]
1727, 1774, 1835, 1874, 1980, 2038
[17]
optical polarizability. In addition, the organic ion group,
[Et4N]+, situated in z-direction tends to enhance the bz
value by a long way. Further study about influence of the
cation on hyperpolarizability is very interesting and signif-
icant, in order to search some cations which tend to en-
hance the b0 value of the molecule. From Table 10, it is
found that the first-order hyperpolarizability of 2 is larger
than that of 7. The complex 2 and 7 belong to non-centro-
symmetric space group and the X-ray crystallography
experiments have showed favorite orientations of the
constituent clusters in a unit cell. The theoretical results
suggest they would be promising candidates for the
second-order NLO effect in medium/far IR region.
The anions of compound 2–4 are the same, [Mo2
(SC6H11)3(CO)6]ꢀ, the only difference is that they contain
the cation: [Et4N]+, [Ph4P]+ and [(CH3)3PhCH2N]+,
respectively. This difference leads to the three compounds
to have different space group: non-centrosymmetric
Pna2(1) and centrosymmetric P2(1)/c, respectively. As the
centrosymmetric space group compound has not second-
order NLO effect, to change the compound’s space group
from centrosymmetric to non-centrosymmetric by intro-
ducing different cations, may be a much more significant
way to compose NLO material.
Fig. 6. Theoretical model and molecular orientation of complex 2.
has been carried out using the finite-field method at HF/
LANL2DZ level. The first hyperpolarizability of the anion
and the molecule of compound 2 have been calculated,
respectively, and the results are shown in Table 10. The b
value can be expressed as
o3E
oF xoF yoF z
bxyz ¼ ꢀLimF !0
;
3. Experimental
X
1
bi ¼
ðbijj þ bjji þ bjijÞ; i; j ¼ x; y; z
3.1. Materials and methods
3
j
b0 ¼ bx þ by þ bz
All experimental procedures including synthetic reac-
tion, structure determination, physical and chemical mea-
surements were carried out under nitrogen atmosphere by
using standard Schlenk technique and all solvents and
reagents were dried and degassed before use. NaC6H11
was prepared by the reaction of C6H11SH with NaOCH3
(which was obtained from the reaction of Na with CH3OH)
in CH3OH. IR spectra were recorded on a Nicolet-Magna
750 Fourier transform IR spectrometer or Digilab FTS-
20E/D-V Fourier transform IR spectrometer. Elemental
analysis was performed on a CARLD ERBA instrumenta-
tion elemental analyzer MOD 1106.
The cation is placed in z-axes in the calculation. The spatial
average value of the first-order hyperpolarizability along z
direction is found quite large, bz = 13 · 10ꢀ30 esu indicat-
ing the potential applications of this cluster for NLO
processes. The theoretical analysis shows that the charge-
transfer inside the [Mo2S3] metal core plays the crucial
role in NLO response and the joint effect of metal core
and organic ligands (C6H11)3s also contribute to nonlinear
Table 10
First-order hyperpolarizability value of the compounds 2 and 7 (b,
10ꢀ30 esu)
Compound
bx
by
bz
b0
3.2. Synthesis of [Et4N]2[Mo2(SC6H11)2(CO)8] (1)
[Mo2(SC6H11)3(CO)6]ꢀ
[Et4N][Mo2(SC6H11)3(CO)6]
[Et4N][W2(SC6H11)3(CO)6]
2
2
0
3
3
6
2
13
5
4
13
8
To the solid mixture of Mo(CO)6 (2.64 g,10 mmol),
Et4NCl (1.655 g,10 mmol) and NaSC6H11 (1.38 g,10 mmol)

1418
Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
was added 50 ml MeCN. The reaction mixture was stirred at
50ꢁC for 24 h resulting in orange-yellow solution with small
amount of white residue in it, accompanied by vigorous CO
evolution. After filtration and concentration, 20 ml of iso-
propanol was added and then the resulting solution was con-
centrated at room temperature until a great deal of yellow
crystalline product came out. After filtering, washed with
acetonitrile–isopropanol and isopropanol in turn and dried
in vacuum, 2.25 g of 1 was obtained (yield 49.6% based on
the Mo(CO)6 used). Anal. Calc. for C36H62N2O8S2 Mo2,
C, 47.63; H, 6.84; N, 3.09; S, 7.06. Found: C, 47.20; H,
6.96; N, 3.52; S, 6.52%; IR (KBr pellet): 1755(s), 1813(s),
1882(s), 1946(s), 1996(s), 2029(m), 2040(m), 2073(w) cmꢀ1
(tco).
evolution. After stirring for 24 h, the resulting brown
solution was evaporated under vacuum to 5 ml. Iso-
propanol (10 ml) was added and the resulting solu-
tion was filtered and the filtrate allowed to stand at
4 ꢁC for several weeks crystalline products were
obtained. Verified by IR and X-ray crystallography,
the product is compound 2.
(d) A solution of compound 1 in MeCN was placed in
refrigerator (at 4 ꢁC). Some yellow crystals formed
in 2 weeks later and the yellow crystals turned to dark
crystals in about 3 months. The dark crystals were
verified to be the compound 2 by IR measurement
and X-ray crystallography.
(e) To a solution of compound 1 (0.0907 g,0.1 mmol) in
MeCN was injected 5.5 ml air, then the solution was
stood at 4 ꢁC for several weeks and crystalline
products were obtained. Verified by IR and X-ray
3.3. Synthesis of [Et4N][Mo2(SC6H11)3(CO)6] (2)
(a) To the solid mixture of Mo2(SC6H11)2(CO)8 [11]
(0.634 g,1 mmol), Et4NCl (0.166 g,1 mmol) and
NaSC6H11 (0.138 g,1 mmol) was added 20 ml ace-
tone. The green solution immediately turned brown,
accompanied with vigorous CO evolution. The reac-
tion mixture was stirred at 50 ꢁC overnight, yielding
a brown solution, which was evaporated under vac-
uum to 5 ml. Isopropanol (10 ml) was added forming
lots of dark precipitate. After filtering, washed with
acetonitrile and dried under vacuum, 0.412 g of 2
was obtained (yield 49.3% based on the Mo2(SC6
H11)2(CO)8 used). Anal. Calc. for C32H53NO6S3Mo2,
C, 45.94, H, 6.34, N, 1.68. Found: C, 46.00, H, 6.35,
N, 1.68%. IR (KBr pellet): 1809(s), 1828(s), 1907(s),
1923(s), 1936(s), 1990(m) cmꢀ1 (tco). The filtrate
was allowed to stand at 4 ꢁC for several days to
obtain crystals for X-ray single-crystal diffraction
analysis.
(b) To the solid mixture of Mo2(SC6H11)2(CO)6(CH3
CN)2[12] (0.323 g,0.5 mmol), Et4NCl (0.083 g, 0.5
mmol) and NaSC6H11 (0.069 g,0.5 mmol) was added
20 ml acetone resulting in grass green solution which
immediately turned brown. The reaction mixture was
stirred at 50 ꢁC overnight, yielding a brown solution
which was evaporated under vacuum to 5 ml. 8 ml
of isopropanol was added forming dark precipitate.
After filtering the filtrate was allowed to stand at
4 ꢁC for several days to obtain crystals for X-ray sin-
gle-crystal diffraction analysis. The resulting dark
precipitate was washed with acetonitrile and dried
under vacuum to yield 0.121 g of pure product, which
had been recognized as compound 2 by IR, elemental
analysis and X-ray crystallography (28.9% yield
based on the Mo2(SC6H11)2(CO)6(CH3CN)2 used).
(c) To the solid mixture of Mo(CO)6 (1.32 g,5 mmol),
Et4NCl (0.83 g,5 mmol) and NaSC6H11 (0.69 g,
5 mmol) was added 30ml MeCN. The reaction mix-
ture was stirred at 85 ꢁC for 10 min, the solution
turned to straw yellow, and then about 30 min later
turned to saffron, accompanied with a lot of CO
crystallography,
compound 2.
the
crystalline
product
is
3.4. Synthesis of [Ph4P][Mo2(SC6H11)3(CO)6] (3)
To the solid mixture of Mo2(SC6H11)2(CO)8 (0.178
g,0.28 mmol), Ph4PBr (0.118 g, 0.28 mmol) and CH3CH2-
CH2COONa (0.031 g, 0.28 mmol) was added 20 ml acetone
resulting in green solution which immediately turned
brown, accompanied with vigorous CO evolution. The
reaction mixture was stirred at 50 ꢁC overnight yielding a
brown solution, which was evaporated under vacuum to
5 ml. Isopropanol (8 ml) was added forming dark precipi-
tate. 0.044 g of pure dark product 3 (yield 15.0% based
on the Mo2(SC6H11)2(CO)8 used) was obtained after filter-
ing, washed with MeCN and dry in vacuum. Anal. Calc.
for C48H53PO6S3Mo2, C, 54.29, H, 5.08. Found: C,
54.70, H, 5.15%. IR (KBr pellet): 1836(m), 1915(m),
1938(m) cmꢀ1 (tco). The mother liquid was stood at 4 ꢁC
for several weeks to obtain single crystals suitable for
X-ray crystallography.
3.5. Synthesis of [(CH3)3PhCH2N][Mo2(SC6H11)3-
(CO)6] (4)
A
solid mixture of Mo(CO)6 (1.32 g, 5 mmol),
(CH3)3PhCH2NBr (1.15 g, 5 mmol) and NaSC6H11 (0.69 g,
5 mmol) in 20 ml MeCN was stirred at 50 ꢁC for 24 h result-
ing in orange-yellow solution with small amount ofwhite res-
idue in it, accompanied with vigorous CO evolution. After
filtration and concentration 10 ml of isopropanol was
added and then the resulting solution was put in refrigerator
(4 ꢁC), 2 weeks later, getting some yellow crystals, about 3
months later, the yellow crystals turned to dark crystals.
The dark crystals were collected and recognized as com-
pound 4 by IR, elemental analysis and X-ray crystallogra-
phy. Anal. Calc. for C34H49NO6S3Mo2, C, 47.67, H, 5.73,
N, 1.64. Found: C, 47.82, H, 5.78, N, 1.58%. IR (KBr pellet):
1828(m), 1915(m), 1936(m) cmꢀ1 (tco).

Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
1419
3.6. Synthesis of [Et4N]2[W2(SC6H11)2(CO)8] (5)
C, 29.20; H, 2.68; S, 7.79. Found: C, 28.88; H, 2.73; S,
7.81%. IR (KBr pellet): 1932(s), 1982(s), 2027(s) cmꢀ1 (tco).
A solid mixture of W(CO)6 (3.52 g, 10 mmol), Et4NCl
(1.65 g, 10 mmol) and NaSC6H11(1.38 g, 10 mmol) in
50 ml MeCN was stirred at 85 ꢁC for 24 h resulting in
orange-yellow solution with small amount of white residue
in it, accompanied with vigorous CO evolution. After cool-
ing to room temperature and filtering off the residue, the fil-
trate was concentrated to 10 ml, then 15 ml of siopropanol
was added forming a great deal of yellow microcrystalline
product, 2.26 g of yellow microcrystalline 5 was obtained.
After filtering, washed with acetonitrile–isopropanol and
isopropanol in turn and dried in vacuum (yield 42% based
on the W(CO)6 used). Anal. Calc. for C36H62N2O8S2 W2,
C, 39.93; H, 5.73; N, 2.59; S, 5.92. Found: C, 39.53; H,
5.81; N, 2.51; S, 5.82%; IR (KBr pellet): 1755(s), 1811(s),
1874(s), 1936(s), 1973(m), 1986(s), 2025(m), 2038(m) cmꢀ1
(tco). The orange-yellow filtrate was concentrated slightly
and then cooled at 4 ꢁC for several days yellow crystals of
5 suitable for X-ray crystallography were obtained.
3.8. Synthesis of [Et4N][W2(SC6H11)3(CO)6] (7)
(a) A solid mixture of W2(SC6H11)2(CO)8 (0.411 g,
5 mmol), Et4NCl (0.083 g, 5 mmol) and NaSC6H11
(0.069 g, 5 mmol) in 20 ml acetone was stirred at
85 ꢁC overnight, resulting in brown solution. The
reaction solution was evaporated under vacuum to
5 ml. 10 ml of isopropanol was added forming some
dark precipitate, 0.15 g of pure product 7 was
obtained after filtering, washed with acetonitrile and
dried under vacuum (yield 30.0% based on the
W2(SC6H11)2(CO)8 used). Anal. Calc. for C32H53
NO6S3W2, C, 36.4; H, 5.02; N, 1.38. Found: C,
36.8; H, 5.05; N, 1.42%. IR (KBr pellet): 1801(s),
1822(s), 1924(s) cmꢀ1 (tco). The mother liquid was
allowed to stand at 4 ꢁC for several days to obtain
crystals for X-ray single-crystal diffraction analysis.
(b) A solution of compound 5 in acetone was placed in
refrigerator (4 ꢁC), 2 weeks later, some yellow crystals
came out and about 2 months later, the yellow crys-
tals turned to dark crystals, which were verified to
be compound 7 by IR and X-ray crystallography.
3.7. Synthesis of [W2(SC6H11)2(CO)8] (6)
A solid mixture of [Et4N]2[W2(SC6H11)2(CO)8] (2.71 g,
2.5 mmol) and I2(0.64 g, 2.5 mmol) in 30 ml toluene was
stirred at room temperature under CO for 5 h resulting in
a dark green solution with white solid in it. After filtering,
the dark green filtrate was concentrated and cooled at 4 ꢁC
for several days, 1.64 g of dark green crystalline product 6
was collected (yield 80.0% based on the [Et4N]2[W2
(SC6H11)2(CO)8] used). Anal. Calc. for C30H33O9S3W3,
3.9. X-ray crystallography
The single crystal samples were mounted on the glass fiber
and coated with epoxy cement. The samples of 1, 2, 5 and 6
were mounted on Siemens Smart CCD diffractometer
Table 11
Crystal data and collection and refinement details for 1 Æ 2CH3CN2, 2–7
Compounds
1 Æ 2CH3CN2
2
3
4
5
6
7
Empirical formula
Formula weight
Crystal system
C
40H68Mo2N4O8S2 C34H53Mo2NO6S3 C48H53Mo2O6PS3
C34H49NO6S3Mo2 C36H62N2O8S2W2 C20H22O6S2W2
C32H53NO6S3W2
1011.63
988.98
Monoclinic
P2(1)/n
835.81
1044.93
855.80
1082.70
Monoclinic
C2c
822.20
Orthorhombic
Pna2(1)
Monoclinic
P2(1)/c
Monoclinic
P2(1)/c
Monoclinic
P2(1)/c
Orthorhombic
Pna2(1)
Space group
Unit cell dimensions
˚
a (A)
14.4322(11)
10.2536(7)
17.1182(13)
100.7310(10)
2488.9(3)
2
20.5805(10)
9.3127(5)
20.2955(10)
90
10.725(4)
26.550(10)
17.808(7)
103.768(4)
4925(3)
4
12.1427(10)
14.1618(10)
23.414(2)
99.752(4)
3968.1(5)
4
15.5168(1)
16.5943(3)
17.0890(3)
101.6290(10)
4309.93(11)
4
18.1140(8)
9.4416(4)
21.4963(10)
90.0950(10)
3674.0(3)
6
20.570(2)
9.280(1)
20.240(4)
90
˚
b (A)
˚
c (A)
b(ꢁ)
Volume (A3)
˚
3889.8(3)
4
3863.6(10)
4
Z
Density (Mg mꢀ1
)
1.320
1.427
1.409
1.433
1.669
2.230
1.739
F(000)
1032
1728
2144
1760
2144
2316
1984
Crystal size (mm)
h Range for
1.00 · 0.40 · 0.24
2.04–25.07
0.40 · 0.15 · 0.20 0.50 · 0.30 · 0.15
0.40 · 0.20 · 0.20 0.80 · 0.60 · 0.52
0.62 · 0.58 · 0.20 0.44 · 0.40 · 0.32
1.98–25.09
2.48–27.48
3.10–25.03
1.82–25.07
1.12–25.06
2.41–27.48
data collection (ꢁ)
Reflections collected
Independent reflections
7890
12476
36803
24915
6764
12433
28619
4381
6570
11126
7007
3811
6462
8712
(Rint = 0.0319)
4381/0/254
(Rint = 0.0545)
6570/1/397
(Rint = 0.0335)
11,266/0/541
(Rint = 0.0443)
7007/0/415
(Rint = 0.0423)
3811/0/266
(Rint = 0.0694)
6462/0/433
(Rint = 0.1112)
8712/1/397
Data/restraints/
parameters
Goodness-of-fit on F2
Final R indices
(I > 2r(I) )
1.072
1.042
1.065
1.075
1.003
1.052
1.002
R = 0.0688,
Rw = 0.1739
0.906 and
ꢀ0.601
R = 0.0469,
Rw = 0.0665
0.488 and
ꢀ 0.367
R = 0.0699,
Rw = 0.1726
2.000 and
ꢀ1.077
R = 0.1042,
Rw = 0.2808
1.698 and
ꢀ2.567
R = 0.0541,
Rw = 0.1180
1.836 and
ꢀ1.878
R = 0.0639,
Rw = 0.1591
2.250 and
ꢀ 2.586
R = 0.0603,
Rw = 0.1165
1.795 and
ꢀ1.739
Largest difference
in peak and hole
ꢀ3
˚
(e A
)

1420
Z. Zhou et al. / Journal of Organometallic Chemistry 692 (2007) 1411–1420
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(1994) 3615;
equipped with a graphite monochromator (Mo Ka radiation
k = 0.71073 A) at 293 K for data collection. The samples of
3, 4 and 7 were mounted on Rigaku Mercury CCD diffrac-
˚
H.W. Hou, H.G. Zheng, H.G. Ang, Y.T. Fan, M.K.M. Low, Y.
Zhu, W.L. Wang, X.O. Xin, W. Ji, H.T. Wong, J. Chem. Soc.,
Dalton Trans. (1999) 2953.
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˚
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The data were corrected for absorption using semi-empirical
scan data. The structures were solved by direct methods and
refined by full-matrix least-squares method. All non-hydro-
gen atoms were refined anisotropically, and hydrogen atoms
were refined as riding model with fixed isotropic U. All cal-
culations were carried out with the Siemens SHELXTL PLUS
package [22] and Rigaku/MSC CRYSTAL CLEAR package
[23], respectively. Crystallographic data for clusters 1–7 are
summarized in Table 11.
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Acknowledgements
We thank NNSFC (the National Natural Science foun-
dation of China) and SKLSC (State Key Laboratory of
Structural Chemistry) for financial support.
[14] Z. Zhou, B. Zhuang, K. Wu, Y. Yao, Chin. J. Struct. Chem. 25
(2006) 1039.
Appendix A. Supplementary material
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(1991) 177.
CCDC 232061, 232060, 243545, 621665, 243543, 243540
and 621666 contain the supplementary crystallographic
data for 1, 2, 3, 4, 5, 6 and 7. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.
ac.uk.
[19] B. Zhuang, H. Sun, G. Pan, L. He, J. Organomet. Chem. 127 (2001)
640.
[20] (a) M. Hohmann, L. Krauth-Siegel, K. Weidenhammer, W. Schulze,
M.L. Ziegler, Z. Anorg. Allg. Chem. 481 (1981) 95;
(b) W. Schulze, M.L. Ziegler, Z. Anorg. Allg. Chem. 481 (1981)
78.
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