2D sheet frameworks constructed from a diruthenium paddlewheel complex and hexamolybdenum halide clusters

Tomonori Sugiura; Koji Ota; Masahiro Ebihara; Takashi Kawamura

doi:10.1016/j.crci.2005.03.018

2D sheet frameworks constructed from a diruthenium paddlewheel complex and hexamolybdenum halide clusters

Tomonori Sugiura ¹ ; Koji Ota ¹ ; Masahiro Ebihara ¹ ; Takashi Kawamura ¹

¹ Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan

Comptes Rendus. Chimie, Volume 8 (2005) no. 11-12, pp. 1760-1765.

Résumés

Anglais
Français

The reaction of [Ru₂(O₂CCMe₃)₄(H₂O)₂]BF₄ with (ⁿBu₄N)₂[(Mo₆Xⁱ₈)X^a₆] (Xⁱ, X^a = Cl, Cl; Cl, Br; Br, Cl) in CH₂Cl₂ afforded 2D sheet structure of [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆Xⁱ₈)X^a₆}]_n·2n CH₂Cl₂ (Xⁱ, X^a = Cl, Cl (1·2 CH₂Cl₂); Cl, Br (2·2 CH₂Cl₂); Br, Cl (3·2 CH₂Cl₂)). 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ are crystallized in isostructural triclinic unit cells and 3·2 CH₂Cl₂ in a monoclinic unit cell. All structures have 2D sheet of square lattices with molybdenum clusters as corners and ruthenium complexes as edges. In 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂, all the Mo₆ and Ru₂ units in a sheet lie in a plane. Diruthenium units in 3·2 CH₂Cl₂ are repeatedly sited above and below the plane of Mo₆ units along the b axis. Then the sheet structure of 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ is flat, while that of 3·2 CH₂Cl₂ is waved. .

La réaction de [Ru₂(O₂CCMe₃)₄(H₂O)₂]BF₄ avec (ⁿBu₄N)₂[(Mo₆X₈)X′₆] (X, X′ = Cl, Cl; Cl, Br; Br, Cl) dans CH₂Cl₂ a conduit à la structure en feuillet 2D de [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆X₈)X'₆}]_n·2n CH₂Cl₂ (X, X′ = Cl, Cl (1·2 CH₂Cl₂); Cl, Br (2·2 CH₂Cl₂); Br, Cl (3·2 CH₂Cl₂)). 1·2 CH₂Cl₂ et 2·2 CH₂Cl₂ cristallisent dans des mailles tricliniques isostructurales, tandis que 3·2 CH₂Cl₂ cristallize dans une maille monoclinique. Toutes les structures présentent des feuillets 2D de réseaux carrés formés par les clusters de molybdène situés aux coins du réseau et les complexes de ruthenium formant les côtés. Dans 1·2 CH₂Cl₂ et 2·2 CH₂Cl₂, tous les motifs Mo₆ et Ru₂ d'un feuillet sont situés dans un plan. Dans 3·2 CH₂Cl₂, les motifs diruthenium sont situés alternativement au-dessus et en dessous du plan formé par les motifs Mo₆ selon l'axe b. Il en résulte que, dans les structures de 1·2 CH₂Cl₂ et 2·2 CH₂Cl₂, les feuillets sont plans, tandis qu'ils sont ondulés dans 3·2 CH₂Cl₂. .

Métadonnées

Reçu le : 2004-09-15
Accepté le : 2005-01-19
Publié le : 2005-07-05

DOI : 10.1016/j.crci.2005.03.018

Keywords: Diruthenium complexes, Molybdenum halide cluster, Metal–metal bonds, X-ray structures, 2-Dimensional structures
Mots clés : Complexes de diruthénium, Halogénures à clusters de molybdène, Liaisons métal–métal, Structures par diffraction X, Structures bidimensionnelles

Affiliations des auteurs :

Tomonori Sugiura ¹ ; Koji Ota ¹ ; Masahiro Ebihara ¹ ; Takashi Kawamura ¹

¹ Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan

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     pages = {1760--1765},
     publisher = {Elsevier},
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Tomonori Sugiura; Koji Ota; Masahiro Ebihara; Takashi Kawamura. 2D sheet frameworks constructed from a diruthenium paddlewheel complex and hexamolybdenum halide clusters. Comptes Rendus. Chimie, Volume 8 (2005) no. 11-12, pp. 1760-1765. doi : 10.1016/j.crci.2005.03.018. https://comptes-rendus.academie-sciences.fr/chimie/articles/10.1016/j.crci.2005.03.018/

Version originale du texte intégral

1 Introduction

One-D to 3D polymerized structures of transition metal complexes have received much attention for the last decade. Not only mononuclear complexes but also various types of clusters, di-, tri-, tetra-, and hexanuclear ones, were used as building blocks. Preparation of a novel polymeric structure with paddlewheel complexes is one of our recent efforts. Paddlewheel complex is a useful building block, because it has rich redox chemistry with various electronic states depending on its bridging ligands, and strained bonding direction to its axial sites. We have synthesized 1 to 3D structures of halide-bridged rhodium or ruthenium paddlewheel complexes. The reaction of a dirhodium or diruthenium cation with halide anion gave only 1D chain structure [1–3]. The reaction of a mixture of cation and neutral complexes with halide linker afforded a 2D structure of [{Rh₂(acam)₄}₃(μ₃-Cl)₂]_n·4 n H₂O [4] and a 3D structure of [{Rh₂(acam)₄}₂(μ₄-I)]_n·6 n H₂O [5]. For the former structure, removal of the crystalline water molecules improved its electric conductivity. On the other hand, the latter has 10⁵ higher conductivity in the hydrated form than in the partially dehydrated one. Other than halide bridges, only a few 2D and 3D polymer structures of paddlewheel dinuclear complexes with organic or anionic mononuclear complex linkers have been reported [6–9].

Hexametal cluster is also a good building block to make multi-dimensional frameworks, because they have a variety of cluster charges and electronic states with M₆Z₈ core (M = Mo, W, Re; Z = halide, chalocogenide). Some network structures with Re₆Z₈ⁿ⁺ (Z = S, Se, Te) [10–12] or W₆S₈ [13] have been reported in the recent years. A novel framework constructed with paddlewheel complexes and hexametal clusters may lead to new physical properties and/or porosity. In this paper, we report synthesis and two types of crystal structures of [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆Xⁱ₈)X^a₆}] (Xⁱ, X^a= Cl, Cl; Cl, Br; Br, Cl).

2 Experimental

2.1 Synthesis

2.1.1 General methods

[Ru₂(O₂CCMe₃)₄Cl(H₂O)] was prepared according to a literature procedure [14] and [Ru₂(O₂CCMe₃)₄(H₂O)₂]BF₄ was synthesized from it by a modification of the method of Barral and coworkers for [Ru₂(O₂CC₆H₄-p-CMe₃)₄(THF)₂]PF₆ [15]. (ⁿBu₄N)₂[(Mo₆X₈)X′₆] (X = Cl, Br; X′ = Cl, Br; I) was obtained by the reaction of Mo₆X₁₂ with Buⁿ₄NX′ in HX′. Dichloromethane, n-hexane and acetonitrile were distilled from CaH₂ before use.

2.1.2 [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆Cl₈)Cl₆}] (1)

A CH₂Cl₂ solution of (ⁿBu₄N)₂[(Mo₆Cl₈)Cl₆] (0.026 g, 0.017 mmol) was added to a CH₂Cl₂ solution of [Ru₂(O₂CCMe₃)₄(H₂O)]PF₆ (0.024 g, 0.033 mmol). Reddish-brown powder was collected, washed with CH₂Cl₂ and dried in vacuo. Yield 0.026 g (69%). Anal. Calc. for C₄₀H₇₂Cl₁₄Mo₆O₁₆Ru₄; C, 21.02; H, 3.18%. Found: C, 21.02; H, 2.96%.

2.1.3 [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆Cl₈)Br₆}] (2)

A CH₂Cl₂ solution of (ⁿBu₄N)₂[(Mo₆Cl₈)Br₆] (0.031 g, 0.017 mmol) was added to a CH₂Cl₂ solution of [Ru₂(O₂CCMe₃)₄(H₂O)]PF₆ (0.022 g, 0.030 mmol). Reddish-brown powder was collected, washed with CH₂Cl₂ and dried in vacuo. Yield 0.024 g (62%). Anal. Calc. for C₄₀H₇₂Br₆Cl₈Mo₆O₁₆Ru₄; C, 18.83; H, 2.84%. Found: C, 18.89; H, 2.67%.

2.1.4 [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆Br₈)Cl₆}] (3)

A CH₂Cl₂ solution of (ⁿBu₄N)₂[(Mo₆Br₈)Cl₆] (0.020 g, 0.011 mmol) was added to a CH₂Cl₂ solution of [Ru₂(O₂CCMe₃)₄(H₂O)]PF₆ (0.016 g, 0.022 mmol). Reddish-brown powder was collected, washed with CH₂Cl₂ and dried in vacuo. Yield 0.020 g (72%). Anal. Calc. for C₄₀H₇₂Br₈Cl₆Mo₆O₁₆Ru₄; C, 18.19; H, 2.75%. Found: C, 17.93; H, 2.74%.

2.2 X-ray structure determination

Crystals of 1·CH₂Cl₂, 2·CH₂Cl₂ and 3·CH₂Cl₂ were obtained as follows: (ⁿBu₄N)₂[(Mo₆Xⁱ₈)X^a₆] was placed in a 6-mm-diameter glass tube and CH₂Cl₂ was gently added to it. Tightly rolled filter paper was put into the tube just above the solution and then a CH₂Cl₂ solution of [Ru₂(O₂CCMe₃)₄(H₂O)]PF₆ was layered. After standing at 15 °C for 3 days, brown crystals were obtained. Diffraction measurements were carried out on a Rigaku AFC7R Mercury CCD diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71069 Å). Because crystals of 1·2 CH₂Cl₂, 2·2 CH₂Cl₂ and 3·2 CH₂Cl₂ easily lost CH₂Cl₂ molecules in a crystal, reflection data were collected at low temperature using a Rigaku XR-TCS-2-050 temperature controller. All structures were solved and refined using the teXsan® crystallographic software package. Scattering factors for neutral atoms were from Cromer and Waber [16] and anomalous dispersion [17] was used. A numerical absorption correction [18] was applied. The structures were solved by direct methods SIR92 [19] and expanded by DIRDIF [20]. Full matrix least-squares refinement was employed. Final least square cycle included non-hydrogen atoms with anisotropic thermal parameters except disordered t-butyl groups were refined as rigid groups. Hydrogen atoms are not included in the refinement. Crystallographic data are summarized in Table 1.

	1·2 CH₂Cl₂	2·2 CH₂Cl₂	3·2 CH₂Cl₂
Chemical formula	C₄₂H₇₆Cl₁₈Mo₆O₁₆Ru₄	C₄₂H₇₆Br₆Cl₁₂Mo₆O₁₆Ru₄	C₄₂H₇₆Br₈Cl₁₀Mo₆O₁₆Ru₄
Formula weight	2455.13	2721.83	2810.73
Crystal system	triclinic	triclinic	monoclinic
Space group	P $\bar{1}$ (No. 2)	P $\bar{1}$ (No. 2)	P2₁/n (No. 14)
a (Å)	14.551 (3)	14.757 (3)	15.374 (6)
b (Å)	14.765 (3)	14.946 (3)	17.851 (7)
c (Å)	20.559 (5)	20.632 (5)	15.364 (6)
α (°)	108.656 (5)	109.179 (5)
β (°)	104.429 (5)	104.016 (7)	91.247 (5)
γ (°)	91.671 (10)	91.26 (1)
V (Å³)	4024 (1)	4144 (1)	4215 (2)
Z	2	2	2
d (calcd) (g cm^–3)	2.026	2.181	2.214
μ (mm^–1)	2.275	4.917	5.721
T (°C)	–40	–100	–40
Reflections collected	33228	34466	34969
Reflections independent	18262	18869	9640
Reflections with I > 2 σ(I)	14028	13194	6003
R_int	0.032	0.044	0.086
R, R_w^a	0.047, 0.106	0.053, 0.107	0.108, 0.287
Residual (min, max) (e Å⁻³)	–1.29, 1.77	–1.93, 2.14	–4.48, 2.70
Goodness-of-fit	1.31	1.13	1.44

^a R = Σ ||Fo| – |Fc||/Σ |Fo| for data with I > 2 σ(I), R_w = [Σ w (Fo² – Fc²)²/Σ w Fo⁴]^1/2 for all data.

3 Results and discussion

In a preliminary experiment, we have tried to make crystals of [{Ru₂(O₂CMe)₄}₂{(Mo₆Cl₈)Cl₆}] in acetonitrile. Mixing of solutions of [Ru₂(O₂CMe)₄]PF₆ and (ⁿBu₄N)₂[(Mo₆Cl₈)Cl₆] did not precipitate crystals. Although evaporation of the solution afforded brown crystals, they include ruthenium complexes with axial acetonitrile ligands and discrete molybdenum clusters. In dichloromethane, reddish-brown powder was precipitated immediately after mixing of solutions of [Ru₂(O₂CCMe₃)₄(H₂O)₂]BF₄ and (ⁿBu₄N)₂[(Mo₆Cl₈)Cl₆]. To make good crystals, very slow mixing of the solutions is needed.

A sheet structure of 1 in 1·2 CH₂Cl₂ is shown in Fig. 1. Structure of 2·2 CH₂Cl₂ is isostructural with 1·2 CH₂Cl₂. There are four independent ruthenium complexes and two independent molybdenum clusters in a unit cell, all of which are at inversion centers (Mo₆: (0, 0, 0) and (0.5, 0, 0.5), Ru₂: (0.5, 0, 0), (0, 0.5, 0), (0, 0, 0.5) and (0.5, 0.5, 0.5)). In each of two independent 2D sheets at c = 0 and 0.5, the centers of Ru₂ complexes and those of Mo₆ clusters are located exactly in the plane. The sheet is made by squares of which corners are molybdenum clusters and edges are ruthenium complexes. Each hexamolybdenum cluster linked to four ruthenium complexes by axial halide ligands. A couple of axial ligands remain as terminal ones. The solvating dichloromethane molecules are sited between the sheets, which are easily lost even at room temperature. The selected distances and angles are summarized in Tables 2 and 3. The distances and angles in two independent sheets are almost identical. The average Ru–Ru distances (1·2 CH₂Cl₂: 2.272 (1) Å, 2·2 CH₂Cl₂: 2.274 (3) Å) are in the range of those observed in other Ru₂(O₂CCMe₃)₄⁺ complexes [21–23]. The Mo–Mo distances in 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ (2.607 (5) and 2.608 (5) Å, respectively) are similar to other hexamolybdenum clusters with capping chloride [24,25]. The ruthenium–halogen distances (2.622 (10) Å for 1·2 CH₂Cl₂ and 2.737 (15) Å for 2·2 CH₂Cl₂) are similar to those observed in diruthenium halide-bridged chain structures [26,27]. The bond distances between molybdenum and bridging axial halides for 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ are 2.480 (19) and 2.613 (21) Å, respectively, which are longer than those between molybdenum and terminal one, 2.395 (1) and 2.548 (4) Å, respectively. These elongated molybdenum–halide distances are also observed in MoCl₂ (= [(Mo₆Cl₈)Cl_4/2Cl₂]) in which each Mo₆Cl₈ unit connects to the four neighboring ones using four outer-chloride as bridges. The Ru–Br–Mo angles for 2 (122.73 (3)–126.24 (3)°) are slightly smaller than the Ru–Cl–Mo angles for 1·2 CH₂Cl₂ (127.08 (6)–131.34 (6)°), which is due to the long Ru–X distance in 2·2 CH₂Cl₂.

Fig. 1
Crystal structure of 1·2 CH₂Cl₂. (a) Top view and (b) side view of the 2D sheet structure. Capping chloro ligands of the hexamolybdenum cluster and methyl carbon atoms are omitted for clarity.

Ru1–Ru1^I	2.2734 (9)	Mo2–Mo3^V	2.6077 (6)
Ru2–Ru2^II	2.2715 (8)	Mo4–Mo5	2.6026 (6)
Ru3–Ru3^III	2.2709 (9)	Mo4–Mo5^VI	2.6116 (7)
Ru4–Ru4^IV	2.2740 (9)	Mo4–Mo6	2.6085 (6)
Ru1–Cl5	2.616 (1)	Mo4–Mo6^VI	2.6004 (7)
Ru2–Cl6	2.616 (1)	Mo5–Mo6	2.6143 (6)
Ru3–Cl12	2.619 (1)	Mo5–Mo6^VI	2.6087 (6)
Ru4–Cl13	2.637 (1)	Mo1–Cl5	2.471 (1)
Mo1–Mo2	2.6135 (7)	Mo2–Cl6	2.482 (1)
Mo1–Mo2^V	2.6007 (6)	Mo3–Cl7	2.396 (2)
Mo1–Mo3	2.6071 (6)	Mo4–Cl12	2.460 (1)
Mo1–Mo3^V	2.6044 (7)	Mo5–Cl13	2.505 (1)
Mo2–Mo3	2.6095 (6)	Mo6–Cl14	2.394 (2)
Ru1^I–Ru1–Cl5	176.25 (4)	Ru1–Cl5–Mo1	127.71 (5)
Ru2^II–Ru2–Cl6	176.82 (5)	Ru2–Cl6–Mo2	131.34 (6)
Ru3^III–Ru3–Cl12	173.32 (4)	Ru3–Cl12–Mo4	127.08 (6)
Ru4^IV–Ru4–Cl13	174.52 (5)	Ru4–Cl13–Mo5	130.44 (6)

^a ^I: 0.5 – x, –y, –z, ^II: –x, 0.5 – y, –z, ^III: –x, –y, 0.5 – z, ^IV: 0.5 – x, 0.5 – y, 0.5 – z, ^V: –x, –y, –z, ^VI: 0.5 – x, –y, 0.5 – z.

Ru1–Ru1^I	2.274 (1)	Mo2–Mo3^V	2.6117 (8)
Ru2–Ru2^II	2.271 (1)	Mo4–Mo5	2.6021 (8)
Ru3–Ru3^III	2.273 (1)	Mo4–Mo5^VI	2.6105 (8)
Ru4–Ru4^IV	2.278 (1)	Mo4–Mo6	2.6088 (7)
Ru1–Br1	2.7207 (9)	Mo4–Mo6^VI	2.6012 (9)
Ru2–Br2	2.7309 (9)	Mo5–Mo6	2.6155 (8)
Ru3–Br4	2.7394 (9)	Mo5–Mo6^VI	2.6108 (8)
Ru4–Br5	2.7562 (9)	Mo1–Br1	2.602 (1)
Mo1–Mo2	2.6113 (8)	Mo2–Br2	2.6119 (9)
Mo1–Mo2^V	2.6002 (8)	Mo3–Br3	2.5505 (9)
Mo1–Mo3	2.6092 (8)	Mo4–Br4	2.594 (1)
Mo1–Mo3^V	2.6050 (9)	Mo5–Br5	2.6422 (9)
Mo2–Mo3	2.6097 (8)	Mo6–Br6	2.5455 (9)
Ru1^I–Ru1–Br1	174.56 (4)	Ru1–Br1–Mo1	123.60 (3)
Ru2^II–Ru2–Br2	177.61 (4)	Ru2–Br2–Mo2	126.24 (3)
Ru3^III–Ru3–Br	172.45 (4)	Ru3–Br–Mo4	122.73 (3)
Ru4^IV–Ru4–Br5	176.24 (4)	Ru4–Br5–Mo5	125.39 (3)

^a ^I: 0.5 – x, –y, –z, ^II: –x, 0.5 – y, –z, ^III: –x, –y, 0.5 – z, ^IV: 0.5 – x, 0.5 – y, 0.5 – z, ^V: –x, –y, –z, ^VI: 0.5 – x, –y, 0.5 – z.

Crystals of 3·2 CH₂Cl₂ includes another type of sheet structure that is shown in Fig. 2. The structure refinement is relatively poor due to the low quality of the crystals of 3·2 CH₂Cl₂. However, it is sufficient to discuss the main feature of the structure. In this structure, the sheet extended on a dihedral plane between a and c axes is also built by squares which consist of four molybdenum clusters as corners and four ruthenium complexes as edges. In the structure of 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂, the sheet is flat, while in the structure of 3·2 CH₂Cl₂, Ru₂ complexes are repeatedly sited above and below a plane made up of Mo₆ clusters, along b-axis. It means that the sheet is waved. Selected bond distances and angles are listed in Table 4. Mo–Mo distances are slightly elongated from those in 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ and are similar to other bromide-capped clusters [28]. The Ru–Ru distance is very similar to those observed in 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂. A largely different structural parameter from 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ is only the Mo–Cl–(Ru₂)–Cl–Mo torsion angle which is 180° in 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂ and 53.6 (3)° in 3·2 CH₂Cl₂.

Fig. 2
Crystal structure of 3·2 CH₂Cl₂. (a) Top view and (b) side view of the 2D sheet structure. Capping bromo ligand of the hexamolybdenum cluster and methyl carbon atoms are omitted for clarity.

Ru1–Ru2	2.273 (2)	Mo1–Mo3′	2.631 (2)
Ru1–Cl1	2.598 (5)	Mo2–Mo3	2.629 (2)
Ru2–Cl2”	2.580 (5)	Mo2–Mo3′	2.626 (2)
Mo1–Mo2	2.623 (2)	Mo1–Cl1	2.450 (4)
Mo1–Mo2′	2.618 (2)	Mo2–Cl2	2.459 (5)
Mo1–Mo3	2.623 (2)	Mo3–Cl3	2.425 (4)
Ru2–Ru1–Cl1	170.7 (1)	Ru1–Cl1–Mo1	128.7 (2)
Ru1–Ru2–Cl2”	170.7 (1)	Ru2′–Cl2–Mo2	128.6 (2)

^a ′: 1 – x, –y, 1–z, ′′–x, 0.5 – y, –z.

Although the reaction of [Ru₂(O₂CCMe₃)₄(H₂O)₂]BF₄ with other Mo₆ clusters (Xⁱ, X^a = Cl, I; Br, Br; Br, I) gave only very small crystals, cell constants of the crystals suggest that these complexes may have a similar flat sheet structure to 1·2 CH₂Cl₂ and 2·2 CH₂Cl₂¹. In the structure of Cs₂[{Fe(H₂O)₂}{Re₆S₈(CN)₆}] [29], sheet structure of [{Fe(H₂O)₂}{Re₆S₈(CN)₆}]^2– in which square is made up of alternating Fe ion and Re clusters is waved as the Fe ions are up and down from a plane of the Re₆ clusters. An amplitude and a period of the wave in this complex are 1.65 and 18.55 Å, respectively, while those of 3· CH₂Cl₂ are 2.27 and 17.85 Å, respectively. The difference of the amplitude is due to the bent Ru–Br–Mo angle compared with the Fe–N–C one.

In summary, two types of structures of [{Ru₂(O₂CCMe₃)₄}₂{(Mo₆Xⁱ₈)X^a₆}], flat and waved sheets are obtained by mixing of the solutions of [Ru₂(O₂CCMe₃)₄(H₂O)₂]⁺ and [(Mo₆Xⁱ₈)X^a₆}]^2–. Unfortunately all crystals degrade by a loss of crystalline dichloromethane molecules. We are investigating to make stable crystals with other paddlewheel complexes and/or molybdenum clusters.

4 Supplementary material

Crystallographic data (excluding structure factors) for the structural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC Nos. 247469–247471 for 1·2 CH₂Cl₂, 2·2 CH₂Cl₂ and 3·2 CH₂Cl₂. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [Fax: +44 1223 33 6033; E-mail: deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk].

¹ Cell constant of the crystals obtained by the reaction of [Ru₂(O₂CCMe₃)₄(H₂O)₂]BF₄ with (ⁿBu₄N)₂[(Mo₆Xⁱ₈)X^a₆] are as follows: Xⁱ, X^a = Cl, I; a = 15.217 (10), b = 15.288 (10), c = 21.14 (1) Å, α = 108.961 (7), β = 104.147 (8), γ = 90.594 (5)°, V = 4487 (4) Å³. Xⁱ, X^a = Br, Br; a = 14.844 (7), b = 14.969 (7), c = 20.65 (1) Å, α = 107.85 (1), β = 104.42 (2), γ = 91.25 (3)°, V = 4205 (3) Å³. Xⁱ, X^a = Br, I; a = 15.25 (1), b = 15.34 (1), c = 21.02 (2) Å, α = 109.45 (3), β = 103.72 (3), γ = 91.14 (6)°, V = 4477 (6) Å³.

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