Synthesis and crystal structures of [W(3,6-dichloro-1,2-benzenedithiolate) 3]n- (n = 1, 2) and [Mo(3,6-dichloro-1,2- benzenedithiolate)3]2-: Dependence of the coordination geometry on the oxidation number and co

Article abstract of DOI:10.1002/ejic.200500074

The novel complexes (Et₄N)₂[W(bdtCl₂) ₃] (1a), (Ph₄P)₂-[W(bdtCl₂) ₃] (1b), (Et₄N)[W(bdtCl₂)₃] (2a), (Ph₄P)[W(bdtCl₂

Full text of DOI:10.1002/ejic.200500074

FULL PAPER
Synthesis and Crystal Structures of [W(3,6-dichloro-1,2-benzenedithiolate)3]n–
(n = 1, 2) and [Mo(3,6-dichloro-1,2-benzenedithiolate)3]2–: Dependence of the
Coordination Geometry on the Oxidation Number and Counter-Cation in
Trigonal-Prismatic and Octahedral Structures
Hideki Sugimoto,*[a] Yuuki Furukawa,[a] Makoto Tarumizu,[a] Hiroyuki Miyake,[a]
Koji Tanaka,[b] and Hiroshi Tsukube[a]
Keywords: Coordination modes / Molybdenum / S ligands / Salt effects / Tungsten
The novel complexes (Et4N)2[W(bdtCl2)3] (1a), (Ph4P)2-
[W(bdtCl2)3] (1b), (Et4N)[W(bdtCl2)3] (2a), (Ph4P)[W(bdtCl2)3] what of an octahedral contribution is included in (Ph4P)2-
with Ph4P+ also resulted in geometrical changes and some-
(2b), (C5NH6)[W(bdtCl2)3] (2c), and (Et3NH)2[Mo(bdtCl2)3]
(3a) (bdtCl2 = 3,6-dichloro-1,2-benzenedithiolate) were pre-
pared and characterized by X-ray crystallographic, UV/Vis
[W(bdtCl2)3] (1b). However, almost the same coordination
structures are present in the series of structures
(Et4N)[W(bdtCl2)3] (2a), (Ph4P)[W(bdtCl2)3] (2b), and
spectroscopic, and electrochemical methods. Versatile geo- (C5NH6)[W(bdtCl2)3] (2c), with an oxidation number of +5.
metrical changes around the tungsten centers were ob- These structures adopt an intermediate geometry between
served. The trigonal-prismatic structure of the tungsten cen-
ter in (Et4N)2[W(bdtCl2)3] (1a) is changed to an intermediate
structure between trigonal prismatic and octahedral upon so-
lid-state oxidation of the complex to (Et4N)[W(bdtCl2)3] (2a).
Replacement of the counter-cation of (Et4N)2[W(bdtCl2)3] (1a)
trigonal prismatic and octahedral. No geometrical change
was observed upon changing the metal center from tungsten
to molybdenum in [M(bdtCl2)3]2– (M = W and Mo).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
According to the classification of Beswick et al., the co-
ordination geometries are found to largely depend on the
nature of the coordinated dithiolene ligands.[7] [M(mnt)3]2–
(M = W and Mo; mnt = 1,2-dicyano-1,2-ethylenedithiolate)
complexes[8] adopt intermediate structures between OCT
and TP [OCT/TP = average of the values for θ/60 and (90 –
φ)/(90 – 55) = 53% for M = Mo and W],[7] whereas
[M(S2C2Me2)3]2– (M = W and Mo; S2C2Me2 = 1,2-di-
methylethylene-1,2-dithiolate) complexes[9] primarily adopt
TP structures (OCT/TP = 1% for M = W and 2% for
Mo).[7] When the bdt ligand is employed (bdt = benzene-
1,2-dithiolate), [W(bdt)3]2– structures largely depend on
these counter-cations. The (Ph4As)2[W(bdt)3] structure[10] is
intermediate between TP and OCT (OCT/TP = 44%),[7]
whereas (Et4N)2[W(bdt)3][11] adopts a TP structure (OCT/
TP = 2%).[7] The oxidation numbers of the metal centers
also have an effect on the geometries. Examples of structur-
ally characterized MIV, MV, and MVI complexes with the
same dithiolene ligands and counter-cations are limited to
(Et4N)n[M(S2C2Me2)3]0/–/2– (M = W and Mo, n = 0, 1, and
Introduction
In recent years, much attention has been directed toward
the synthesis of metal complexes containing dithiolene li-
gands. This interest is primarily due to their utility in mag-
netic materials, superconductors, nonlinear optical materi-
als, luminescent sensors, and enzyme catalytic centers.[1–4]
The synthetic routes to tungsten and molybdenum com-
plexes with dithiolene ligands have been extensively devel-
oped,[5,6] and their tris(dithiolene) complexes have been well
characterized.[7] These tris(dithiolene) complexes show
interesting characteristics in terms of both reversible elec-
tron-transfer reactions and geometrical variations around
the metal centers. Although six-coordinate metal complexes
generally exhibit an octahedral coordination geometry to
minimize ligand interactions, it is well known that tris(dithi-
olene) complexes of molybdenum and tungsten can adopt
both octahedral (OCT) and trigonal-prismatic (TP) struc-
tures (Scheme S1 in the Supporting Information).[7]
[a] Department of Chemistry, Graduate School of Science, Osaka
City University,
2),[9,12] but all the six complexes adopt near TP geome-
Sumiyoshi-ku 3-3-138, Osaka 558-8585, Japan
Fax: +81-6-6605-2522
tries.[7] On the other hand, [W(bdt)3]0/–/2–
and
[10–14]
[W(S2C2Ph2)3]0/– (S2C2Ph2 = 1,2-phenylethylene-1,2-dithiol-
ate)[15] structures adopt variable geometries ranging from
OCT/TP = 0% to OCT/TP = 62% (former), and from 39%
to 2% (latter).[7] Because these complexes have different
E-mail: sugimoto@sci.osaka-cu.ac.jp
[b] Institute for Molecular Science,
Higashiyama, Okazaki, 444–8787, Japan
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
3088
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejic.200500074
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Trigonal-Prismatic and Octahedral [W(bdtCl2)3]n– and [Mo(bdtCl2)3]2–
FULL PAPER
Scheme 1. Diagram showing geometrical changes.
counter-cations, including Me2Ph2P+, Me4N+, Et4N+, nium cation stacks between the aromatic phenyls of two
Ph4As+, and PhCH2(Et)3N+, and the effects of the oxi- anions (ca. 3.5 Å) to form a chain structure (not shown).
dation number and counter-cation on the geometry still re- The θ and φ values (see Experimental Section) given in
main unclear, we have systematically characterized a series Scheme S1 are good indications for a geometry between TP
of [M(dithiolene)3]–/2– (M = W and Mo) complexes contain- (θ = 0° and φ = 90°) and OCT (θ = 60° and φ Ϸ 55°). The
ing the same counter-cations but weaker electron-donating values of our new complexes and related complexes taken
dithiolene ligands than S2C2Me2. The structural compari- from the literature are listed in Table 1.
son between the tris(bdtCl2) complexes of tungsten and mo-
lybdenum (bdtCl2 = 3,6-dichloro-1,2-benzenedithiolate)
(Et4N)2[W(bdtCl2)3] (1a), (Ph4P)2[W(bdtCl2)3] (1b),
(Et4N)[W(bdtCl2)3]
(2a),
(Ph4P)[W(bdtCl2)3]
(2b),
(C5NH6)[W(bdtCl2)3] (2c), and (Et3HN)2[Mo(bdtCl2)3] (3a)
reveals new insights into the factors governing the struc-
tures of tris(dithiolene) complexes (Scheme 1).
Results and Discussion
Structural Characterization
Figure 1. Structure of anion part of 1a with 50% probability ther-
mal ellipsoids. Selected bond lengths [Å] and angles [°]: W(1)–S(1)
2.374(5), W(1)–S(2) 2.381(5), W(1)–S(3) 2.382(4), W(1)–S(4)
Figures 1, 2, and 3 show the crystal structures of the an-
ionic tungsten(iv) complexes 1a and 1b, and the molybde- 2.358(5), W(1)–S(5) 2.372(4), W(1)–S(6), 2.378(5); S(2)–W(1)–S(1)
81.2(2), S(4)–W(1)–S(1) 141.3(2), S(6)–W(1)–S(1) 131.1(2), S(3)–
W(1)–S(2) 128.4(2), S(4)–W(1)–S(2) 82.9(2), S(5)–W(1)–S(2)
num(iv) complex 3a, respectively, and Figures 4, 5, and 6
show those of the tungsten(v) complexes 2a–2c, respec-
139.5(2),S(4)–W(1)–S(3) 81.4(2), S(6)–W(1)–S(3) 141.2(2), S(5)–
tively. The metal centers of all anions are coordinated to six
W(1)–S(4) 130.6(2), S(6)–W(1)–S(5) 81.3(2).
sulfur atoms from three bdtCl2 ligands, and all the anions
interact with the counter-cations through C–H···S bonds
The tungsten(iv) center in 1a adopts an almost TP struc-
(3–3.6 Å). The crystal structure of 2c reveals that the pyridi- ture (θ = 7°, φ = 86°, and OCT/TP = 12%; Scheme S1).
Eur. J. Inorg. Chem. 2005, 3088–3092
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H. Sugimoto, Y. Furukawa, M. Tarumizu, H. Miyake, K. Tanaka, H. Tsukube
FULL PAPER
Figure 5. Structure of anion part of 2b with 50% probability ther-
mal ellipsoids. Selected bond lengths [Å] and angles [°]: W(1)–S(1)
2.389(3), W(1)–S(2) 2.367(2), W(1)–S(3) 2.382(2), W(1)–S(4)
2.382(2), W(1)–S(5) 2.366(2), W(1)–S(6), 2.391(2); S(2)–W(1)–S(1)
82.29(9), S(4)–W(1)–S(1) 111.27(9), S(6)–W(1)–S(1) 154.75(9),
S(3)–W(1)–S(2) 155.6(1), S(4)–W(1)–S(2) 82.26(9), S(5)–W(1)–S(2)
114.62(9), S(4)–W(1)–S(3) 82.67(8), S(6)–W(1)–S(3) 113.16(9),
S(5)–W(1)–S(4) 155.62(8), S(6)–W(1)–S(5) 85.12(8).
Figure 2. Structures of anion part of 1b with 50% probability ther-
mal ellipsoids. Selected bond lengths [Å] and angles [°]: W(1)–S(1)
2.380(1), W(1)–S(2) 2.393(1), W(1)–S(3) 2.379(2); S(1)–W(1)–S(1)*
150.63(6), S(2)–W(1)–S(1) 82.62(4), S(3)*–W(1)–S(1) 119.00(5),
S(3)*–W(1)–S(2) 153.02(5), S(3)–W(1)–S(2)* 153.02(5), S(3)*–
W(1)–S(3) 82.01(6).
Figure 3. Structure of anion part of 3a with 50% probability ther-
mal ellipsoids. Selected bond lengths [Å] and angles [°]: Mo(1)–S(1)
2.383(5), Mo(1)–S(2) 2.384(4), Mo(1)–S(3) 2.394(4), Mo(1)–S(4)
2.380(5),Mo(1)–S(5) 2.409(4), Mo(1)–S(6), 2.378(5); S(2)–Mo(1)–
S(1) 81.7(2), S(4)–Mo(1)–S(1) 131.7(2), S(6)–Mo(1)–S(1) 136.7(2),
S(3)–Mo(1)–S(2) 137.1(2), S(4)–Mo(1)–S(2) 81.7(2), S(5)–Mo(1)–
S(2) 134.4(2),S(4)–Mo(1)–S(3) 80.5(2), S(6)–Mo(1)–S(3) 133.6(2),
S(5)–Mo(1)–S(4) 137.8(2), S(6)–Mo(1)–S(5) 80.2(2).
Figure 6. Structure of anion part of 2c with 50% probability ther-
mal ellipsoids. Selected bond lengths [Å] and angles [°]: W(1)–S(1)
2.385(3), W(1)–S(2) 2.385(3), W(1)–S(3) 2.378(3), W(1)–S(4)
2.379(3), W(1)–S(5) 2.388(3), W(1)–S(6), 2.375(3); S(2)–W(1)–S(1)
82.3(1), S(4)–W(1)–S(1) 114.4(1), S(6)–W(1)–S(1) 157.0(1), S(3)–
W(1)–S(2) 157.6(1), S(4)–W(1)–S(2) 84.9(1), S(5)–W(1)–S(2)
110.6(1), S(4)–W(1)–S(3) 82.3(1), S(6)–W(1)–S(3) 111.9(1), S(5)–
W(1)–S(4) 157.0(1), S(6)–W(1)–S(5) 81.8(1).
Table 1. Comparison of θ [°], φ [°], and OCT/Tp [%][a] values of 1a,
1b, 2a–2c, 3a, and related complexes.
θ
φ
OCT/Tp[a] Ref.
Trigonal prism
Octahedral
0
60
7
23
33
27
30
2
90
Ϸ55
86
76
70
73
72
88
87
0
100
12
39
56
45
50
5
[b]
(Et4N)2[W(bdtCl2)3] (1a)
(Ph4P)2[W(bdtCl2)3] (1b)
(Et4N)[W(bdtCl2)3] (2a)
(Ph4P)[W(bdtCl2)3] (2b)
(C5NH6)[W(bdtCl2)3] (2c)
(Et3NH)2[Mo(bdtCl2)3] (3a)
(Et4N)2[W(bdt)3]
[b]
[b]
[b]
[b]
Figure 4. Structure of anion part of 2a with 50% probability ther-
mal ellipsoids. Selected bond lengths [Å] and angles [°]: W(1)–S(1)
2.369(3), W(1)–S(2) 2.382(3), W(1)–S(3) 2.382(3), W(1)–S(4)
2.382(3), W(1)–S(5) 2.390(3), W(1)–S(6), 2.382(3); S(2)–W(1)–S(1)
82.69(9), S(4)–W(1)–S(1) 110.7(1), S(6)–W(1)–S(1) 157.6(1), S(3)–
W(1)–S(2) 159.0(1), S(4)–W(1)–S(2) 84.51(9), S(5)–W(1)–S(2)
111.8(1),S(4)–W(1)–S(3) 82.38(9), S(6)–W(1)–S(3) 109.6(1), S(5)–
W(1)–S(4)160.0(1), S(6)–W(1)–S(5) 82.5(1).
[b]
[7,11]
4
2
[7,10]
(Ph4As)2[W(bdt)3]
(Me2Ph2P)[W(bdt)3]
(Ph4As)2[W(mnt)3]
23
30
28
76
72
73
44
62
53
[7,13]
[7,8]
[a] Average of the values for θ/60 and (90 – φ)/(90 – 55). [b] This
work.
Interestingly, the coordination geometry of TP changes to the two metal centers having the same oxidation number.
an intermediate structure between TP and OCT upon re- Similar geometrical changes were observed between
placing the Et4N+ cations of 1a with the larger Ph4P+ cat- (Et4N)2[W(bdt)3][11] (θ = 4°, φ = 87°, and OCT/TP = 2%)[7]
ions in 1b (θ = 23°, φ = 76°, and OCT/TP = 39%), despite and (Ph4As)2[W(bdt)3][10] (θ = 23°, φ = 76°, and OCT/
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Trigonal-Prismatic and Octahedral [W(bdtCl2)3]n– and [Mo(bdtCl2)3]2–
FULL PAPER
TP = 44%).[7] In both series of bdtCl2 and bdt complexes
the smaller counter-cation favors a near TP structure,
whereas the larger counter-cation results in an intermediate
structure between TP and OCT. Furthermore, when the
tungsten(iv) is oxidized (see 1a vs. 2a) the coordination ge-
ometry changes considerably from an almost TP structure
to an intermediate structure between TP and OCT (θ = 33°,
φ = 70°, and OCT/TP = 56%). However, in complexes hav-
Et3N (0.75 mL, 0.0047 mol) was added slowly to a suspension of
[WOCl3(THF)2] (0.45 g, 0.001 mol) in CH3CN (10 mL) at –40 °C.
The solution was warmed to room temperature and stirred for
30 min. The obtained purple suspension was filtered and the filtrate
was concentrated to about 6 mL. Addition of Et4NI (0.38 g,
0.0015 mol) in CH3OH (15 mL) to the solution gave a purple pre-
cipitate. The purple solid was dissolved in the minimum amount of
acetone and purified by passing through an alumina column using
acetone/CH3OH as the eluent. A red component of (Et4N)2-
[W(bdtCl2)3] was eluted first and then a purple component of
+
ing the larger PPh4 cation, oxidation from 1b to 2b (θ =
27°, φ = 73°, and OCT/TP = 45%) results in only slight (Et4N)[W(bdtCl2)3] was separated. Each solution was evaporated
to dryness.
changes in the coordination geometry.
The θ and φ values of 2c (θ = 30°, φ = 72°, and OCT/TP
= 50%) are similar to those for 2a and 2b, indicating that,
in tungsten(v) bdtCl2 complexes, geometrical changes rarely
occur upon changing the counter-cations. Although
(Me2Ph2P)[W(bdt)3][13] was found to adopt an intermediate
structure between TP and OCT (θ = 30°, φ = 72°, and OCT/
TP = 62%),[7] the structures of (Me2Ph2P)2[W(bdt)3] and
[W(bdt)3]–, which have different counter-cations from
Me2Ph2P+, have not been reported. The present results indi-
cate that counter-cations significantly influence the coordi-
nation geometries in tungsten(iv) complexes, while little ef-
fect is observed in tungsten(v) complexes. Further, the ge-
ometries of complexes with small cations such as Et4N+ are
sensitive to the oxidation state of the metal. The factors
governing those geometrical changes have not been iden-
tified at this stage, but both packing forces in the crystals
and matching of ligand orbitals and metal d orbitals in en-
ergies may be important for this series of tungsten bdtCl2
complexes. The molybdenum center in 3a takes an almost
TP structure (θ = 2°, φ = 88°, and OCT/TP = 5%), suggest-
ing that replacement of tungsten with molybdenum in
[M(bdtCl2)3]2– complexes does not influence the coordina-
tion geometry around the metal centers.
1a: Yield: 0.38 g (35%). C34H46Cl6N2S6W (1071.7): calcd. C 38.11,
H 4.33, N 2.61. found C 37.76, H 4.08, N 2.56. UV/Vis (CH3CN):
λmax (ε) = 470 nm (8300 m–1 cm–1), 535 (4700).
2a: Yield 0.14 g (15%). C26H26Cl6NS6W (941.46): calcd. C 33.17,
H 2.78, N 1.49; found C 33.41, H 2.70, N 1.54. UV/Vis (CH3CN):
λmax (ε) = 360 nm (9400 m–1 cm–1), 540 (5200), 650 (sh). ESI-MS:
m/z = 811.5 [M]–. CV (V vs. SCE in CH3CN): –0.19 (reversible),
+0.47 (reversible).
(Ph4P)2[W(bdtCl2)3] (1b): The complex was prepared in the same
way as 1a except that PPh4Br was employed instead of Et4NI.
Yield: 0.58 g (39%). C66H46Cl6P2S6W (1490.0): calcd. C 53.20, H
3.11; found C 53.46, H 3.41.
(Ph4P)[W(bdtCl2)3] (2b):
A methanolic solution (10 mL) of
H2bdtCl2 (0.07 g, 0.0003 mol) was added to WO2Cl2 (0.03 g,
0.0001 mol) and a purple solution was obtained after 24 h. After
filtration, Ph4PBr (0.042 g, 0.0001 mol) was added to the obtained
purple solution to give deep-purple microcrystals. The precipitate
was collected by filtration and dried in air. Yield: 0.07 g (61%).
C42H26Cl6PS6W (1150.6): calcd. C 43.84, H 2.28; found C 43.98,
H 2.51.
(C5NH6)[W(bdtCl2)3]·2CH3OH (2c)·2CH3OH: This complex was
prepared in the same way as 2b except that pyridinium trifluorome-
thanesulfonate was used instead of Ph4PBr. Yield: 0.05 g (54%).
C25H20Cl6NO2S6W (955.37): calcd. C 31.43, H 2.11, N 1.47; found
C 31.59, H 2.38, N 1.51.
Conclusions
(Et4N)2[Mo(bdtCl2)3] (3): [MoO2Cl2] (0.04 g, 0.2 mmol) was added
to a THF solution (10 mL) of H2bdtCl2 (0.13 g, 0.6 mmol) and
the solution was stirred for 3 h. The obtained green solution was
concentrated to 5 mL and purified by passing through a neutral
alumina column using acetone/CH3OH (1:4) as an eluent. A blue
band was collected and concentrated to 5 mL, and addition of
Et4NI (0.05 g, 0.19 mmol) gave a blue microcrystalline powder,
which was collected by filtration and dried in vacuo. Yield: 0.004 g
(21%). C34H46Cl6MoNS6 (983.80): calcd. C 41.51, H 4.71, N 2.85;
found C 41.39, H 4.65, N 2.87. UV/Vis (CH3CN): λmax (ε) =
284 nm (46800 m–1 cm–1), 352 (20500), 574 (11000). CV (V vs. SCE
in CH3CN): +0.03 (reversible), +0.62 (reversible).
A series of tungsten(iv) and -(v) tris(3,6-dichloro-1,2-
benzenedithiolate) complexes with Et4N+, Ph4P+, and pyri-
dinium cations as well as a molybdenum(iv) derivative with
an Et4N+ cation have been presented. Solid-state crystallo-
graphic analysis reveals that the coordination geometries of
the six-coordinate tungsten(iv) centers depend significantly
on the sizes of the counter-cations, with a trigonal-prismatic
geometry for the smaller Et4N+ (1a) and an intermediate
structure between a trigonal prism and an octahedral geom-
etry for the larger Ph4P+ (1b). On the other hand, tung-
sten(v) complexes including Et4N+, Ph4P+, and pyridinium
cations (2a–2c) adopt almost the same intermediate struc-
tures. Furthermore, the coordination geometries around
tungsten in Et4N+ complexes are dependent on the oxi-
dation state of the metal (trigonal prism for WIV and inter-
mediate for WV), except in the case of Ph4P+ complexes.
Calculation of θ and φ Angles (°) in Crystal Structures: The θ angle
was calculated as the torsion angle between the two S atoms of
bdtCl2 with respect to the aligned centers of gravity between the
S1, S3, and S5, and S2, S4, and S6 atoms, respectively. The φ angle
was calculated as the dihedral angle between the SMS groupings
of the bound ligands (S1MS2, S3MS4, S5MS6; M = Mo and W)
and the trigonal planes S1S3S5 and S2S4S6, according to ref.[7] S1–
S6 are labeled in Scheme S1 (see Supporting Information).
Averaged values are employed in this paper. The percentage (OCT/
TP) used for the OCT and TP is the average of the values θ/60 and
(90 – φ)/(90 – 55), respectively.
Experimental Section
(Et4N)2[W(bdtCl2)3] (1a) and (Et4N)[W(bdtCl2)3] (2a): A CH3CN
solution (10 mL) containing H2bdtCl2 (0.50 g, 0.0025 mol) and
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H. Sugimoto, Y. Furukawa, M. Tarumizu, H. Miyake, K. Tanaka, H. Tsukube
Other Measurements: Cyclic voltammograms were recorded at Analysis Software, Ver. 3.6.0.[18] Further crystal data and agree-
FULL PAPER
100 mVs–1 with a Hokuto HZ-3000. The working and counter elec-
trodes were a glassy-carbon disk and a platinum wire, respectively.
The sample solutions were deoxygenated with a stream of N2. The
reference electrode used was an SCE. Electronic spectra were re-
corded with a Shimazu-U2550 spectrometer at 20 °C.
ment factors are listed in Tables 2 and 3.
CCDC-261315–261320 (for 1a, 1b, 2a, 2b, 2c, and 3a, respectively)
contain the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Center via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information: Description of the θ and φ angles (Scheme
S1), and detailed bond lengths [Å] and angles [°] around the metal
centers (Tables S1–S6).
X-ray Crystallographic Study: Single crystals of 1a, 1b, 2a, 2b, and
2c were recrystallized from acetone, hexane, acetonitrile/diethyl
ether, and methanol, respectively. Although a single crystal of 3
was not obtained by recrystallization, a single crystal of 3a was
obtained by adding Et3NHBr to a solution of 3 in CH3CN. Each
single crystal obtained was mounted on top of a glass fiber. X-ray
data of the complexes were collected with graphite-monochromated
Mo-Kα radiation on a Rigaku/MSC Mercury CCD diffractometer.
The structures were solved by direct methods (SIR-97)[16] and ex-
panded using DIRDIF 99.[17] The structures were refined aniso-
tropically by full-matrix least-squares on F2. The non-hydrogen
atoms in all structures were attached at idealized positions on the
carbon atoms and not refined. All structures converted in the final
stages of refinement showed no movement in the atom positions.
All calculations were performed with Single Crystal Structure
Acknowledgments
This work was partly supported by a Grant for Scientific Research
(no. 16750052 to H.S.) from the Japan Society for Promotion of
Science and by CREST of the Japan Science and Technology Ag-
ency (JST).
[1] C. Faulmann, P. Cassoux, Progress in Inorganic Chemistry: So-
lid-State Properties (Electronic, Magnetic, Optical) of Dithi-
olene Complex-Based Compounds (Ed.: E. I. Stiefel), John
Wiley & Sons, New Jersey, 2004, 52, 399–489.
[2] S. D. Cummings, R. Eisenberg, Progress in Inorganic Chemis-
try: Luminescence and Photochemistry of Metal Dithiolene
Complexes (Ed.: E. I. Stiefel), John Wiley & Sons, New Jersey,
2004, 52, 315–367.
[3] S. J. N. Burgmayer, Progress in Inorganic Chemistry: Dithiolene
in Biology (Ed.: E. I. Stiefel), John Wiley & Sons, New Jersey,
2004, 52, 491–537.
[4] J. McMaster, J. M. Tunney, C. D. Garner, Progress in Inorganic
Chemistry: Chemical Analogs of the Catalytic Centers of Mo-
lybdenum and Tungsten Dithiolene Containing Enzymes (Ed.:
E. I. Stiefel), John Wiley & Sons, New Jersey, 2004, 52, 539–
583.
[5] J. A. McCleverty, Prog. Inorg. Chem. 1968, 10, 49–221.
[6] A. Davison, R. H. Holm, Inorg. Synth. 1967, 10, 8–26.
[7] C. L. Beswick, J. M. Schulman, E. I. Stiefel, Progress in Inor-
ganic Chemistry: Structures and Structural Trends in Homolep-
tic Dithiolene Complexes (Ed.: E. I. Stiefel), John Wiley & Sons,
New Jersey, 2004, 52, 55–110.
[8] G. F. Brown, E. I. Stiefel, Inorg. Chem. 1973, 12, 2140–2147.
[9] D. V. Fomitchev, B. S. Lim, R. H. Holm, Inorg. Chem. 2001,
40, 645–654.
Table 2. Crystallographic data for 1a, 1b, and 3a.
1a
1b
3a
Formula
Molecular mass 1071.68
C34H46Cl6N2S6W C66H46Cl6P2S6W C30H38Cl6N2MoS6
1489.96
–150
927.66
–150
Temp. [°C]
Crystal system
Space group
a [Å]
–130
orthorhombic
P212121
14.580(2)
15.283(2)
19.227(2)
90
orthorhombic
Fdd2
24.051(1)
32.358(2)
15.3131(9)
90
orthorhombic
P212121
14.363(3)
15.971(5)
16.641(4)
90
b [Å]
c [Å]
α [°]
β [°]
90
90
90
γ [°]
90
4284.3(8)
4
1.661
9244
90
90
V [Å3]
Z
11917.2(12)
8
1.660
8320
3799.0(17)
4
1.622
Dcalcd. [gcm–3
Unique data
]
2743
Observed data
R [%]
5908
7.5
7321
4.0
2310
8.1
wR [%]
17.2
9.8
21.9
GOF
1.062
1.00
1.084
[10] F. Knoch, D. Sellmann, W. Kem, Z. Kristallogr. 1993, 250,
300–302.
[11] C. Lorber, J. P. Donahue, C. A. Goddard, E. Nordlander, R. H.
Holm, J. Am. Chem. Soc. 1998, 120, 8102–8112.
[12] B. S. Lim, J. P. Donahue, R. H. Holm, Inorg. Chem. 2000, 39,
263–273.
Table 3. Crystallographic data for 2a–2c.
2a
2b
2c
[13] T. E. Burrow, R. H. Morris, A. Hills, D. L. Hughes, R. L. Rich-
ards, Acta Crystallogr., Sect. C 1993, 49, 1591–1594.
[14] H. Huynh, T. Lugger, F. E. Hahn, Eur. J. Inorg. Chem. 2002,
3007–3009.
Formula
Molecular mass
Temp. [°C]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C26H26Cl6NS6W C39H42Cl6PS6W C25H20Cl6NS6W
941.43
–120
monoclinic
C2/c
1135.67
–160
monoclinic
P21/c
955.37
–160
monoclinic
P21/n
[15] C. A. Goddard, R. H. Holm, Inorg. Chem. 1999, 38, 5389–
17.15(8)
19.31(8)
20.22(10)
90
92.57(8)
90
22.850(2)
13.6306(9)
27.388(2)
90
94.297(4)
90
10.391(5)
20.941(10)
15.497(8)
90
106.349(6)
90
5398.
[16] A. Altomare, M. Burla, M. Camalli, G. Cascarano, C. Giacov-
azzo, A. Guagliardi, A. Moliterni, G. Polidori, R. Spagna, J.
Appl. Crystallogr. 1999, 32, 115–119.
[17] P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R.
de Gelder, R. Israel, J. M. M. Smits, 1999. The DIRDIF-99 pro-
gram system, Technical Report of the Crystallography Labora-
tory, University of Nijmegen, The Netherlands.
[18] Crystal Structure Analysis Package, Rigaku and Rigaku/MSC,
2000–2004, 9009 New Trails Dr., The Woodlands, TX 77381,
USA.
γ [°]
V [Å3]
6688.1(52)
8
1.870
7564
5893
7.2
8506.4(11)
4
1.766
23578
10962
4.9
3235.9(27)
4
1.961
7383
4491
Z
Dcalcd. [gcm–3
]
Unique data
Observed data
R [%]
wR [%]
GOF
6.5
19.2
1.346
12.7
0.931
14.7
0.992
Received January 24, 2005
Published Online: June 28, 2005
3092
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 3088–3092