Tris(tetra­butyl­ammonium) hexa­kis­(tert-butane­thiol­ato-κS)hepta-μ3-chlorido-μ3-sulfido-hexa­molybdate dihydrate

Petrov, P.A.; Naumov, D.Y.; Konchenko, S.N.

doi:10.1107/S1600536812007416

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m333-m334

doi:10.1107/S1600536812007416

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Tris(tetrabutylammonium) hexakis(tert-butanethiolato-κS)hepta-μ₃-chlorido-μ₃-sulfido-hexamolybdate dihydrate

Pavel A. Petrov,^a ^* Dmitry Yu. Naumov ^a and Sergey N. Konchenko ^a

^aNikolaev Institute of Inorganic Chemistry, SB Russian Academy of Sciences, Akademician Lavrentiev prospekt 3, Novosibirsk 90, 630090, Russian Federation, and, Novosibirsk State University, Pirogov street 2, Novosibirsk 90, 630090, Russian Federation
^*Correspondence e-mail: panah@mail.ru

(Received 1 February 2012; accepted 19 February 2012; online 24 February 2012)

The octahedral cluster core of the anion in the structure of the title compound, (C₁₆H₃₆N)₃[Mo₆(C₄H₉S)₆(μ₃-Cl)₇(μ₃-S)]·2H₂O, has -3 site symmetry. Two μ₃-Cl atoms fully occupy positions in the cluster core, while the remaining six positions are statistically occupied by Cl and S atoms in a 1:5 ratio. The fully occupied Cl-atom positions are located on sites with 3 symmetry, and the N atom of tetrabutylammonium cation is located on a site with 2 symmetry. The structure contains also two disordered solvent water molecules, one of which is located on a threefold rotation axis and the other in a general position, both with an occupancy of 0.25. The water molecules are localized in cavities formed by the tetrabutylammonium cations and the tert-butanethiolate groups. The metal clusters are stacked in a cubic close packing arrangement along [001].

Related literature

For a review of octahedral halogen-bridged metal clusters, see: Prokopuk & Shryver (1998 ). For synthesis and structures of related halogen/chalcogen clusters, see: Abramov et al. (2009 ); Ebihara et al. (1988 ); Ebihara, Imai et al. (1995 ); Ebihara, Toriumi et al. (1995 ); Michel & McCarley (1982 ); Nocera & Gray (1984 ). For a related transformation of tBuS⁻, see: Petrov et al. (2010 ). For synthesis and structures of related clusters with sulfur-substituted halogen atoms, see: Schoonover et al. (1996 ); Szczepura et al. (2008 ).

Experimental

Crystal data

(C₁₆H₃₆N)₃[Mo₆(C₄H₉S)₆Cl₇S]·2H₂O
M_r = 2154.29
Trigonal, $[R \overline 3c ]$
a = 18.7481 (5) Å
c = 52.4233 (12) Å
V = 15957.7 (7) Å³
Z = 6
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 150 K
0.42 × 0.35 × 0.23 mm

Data collection

Bruker–Nonius X8 APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.670, T_max = 0.797
36925 measured reflections
3637 independent reflections
3092 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.125
S = 1.14
3637 reflections
161 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Selected bond lengths (Å)

Mo1—Mo1ⁱ	2.6067 (4)
Mo1—Mo1ⁱⁱ	2.6328 (5)
Mo1—S1	2.5158 (9)
Mo1—S2ⁱⁱⁱ	2.4792 (9)
Mo1—S2^iv	2.4842 (9)
Mo1—Cl1	2.5054 (10)
Mo1—Cl2	2.4801 (9)
Mo1—Cl2ⁱⁱⁱ	2.4792 (9)
Mo1—Cl2^iv	2.4842 (9)
Symmetry codes: (i) y, -x+y, -z; (ii) -x+y, -x, z; (iii) -y, x-y, z; (iv) x-y, x, -z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006 ) and POV-RAY (Persistence of Vision, 2004 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007416/wm2589sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007416/wm2589Isup2.hkl

checkCIF report

Comment top

The octahedral clusters of early transition metals are often regarded as precursors of functional materials with redox and/or luminescent properties. The advantage of halide-bridged clusters [Mo₆(µ₃-X)₈X₆]^2- (X = halogen) is the ability of tuning the electronic structure and the properties of the cluster core by step-by-step exchange of the terminal X atoms. The exchange of the µ₃-bridging X atoms is also possible; however, reactions of this type are less common. The halogen-chalcogen clusters with one or two chalcogen atoms (or their mixtures) were obtained in the reactions of [Mo₆(µ₃-X)₈X₆]^2- with NaSH, NaSeH or in situ-generated H₂Se (Michel & McCarley, 1982; Ebihara et al., 1988; Ebihara, Imai et al., 1995; Ebihara, Toriumi et al., 1995; Abramov et al., 2009).

Recently, the reaction of [Mo₆(µ₃-X)₈(OMe)₆]^2- with excess EtSH was reported leading to the smooth substitution of the terminal methoxides to ethanethiolate groups. The latter can be further substituted by other SR^- groups where R = butyl, benzyl or 3-indolyl (Szczepura et al., 2008). Our attempt was aimed to prove if the reaction of [Mo₆(µ₃-X)₈X₆]^2- with ^tBuSNa would stop on the substitution of the terminal X atoms, or would result in a core rearrangement as well. Previously, ^tBuS^- was reported to be the source of the S^2- anion (see, for example: Petrov et al. 2010).

The presence of three tetrabutylammonium cations designates the charge of the cluster core. Keeping in mind the high oxidation potential of the [Mo₆(µ₃-Cl)₈Cl₆]^3-/2- pair (1.53 V in MeCN versus SCE, Nocera & Gray, 1984) one would formulate the cluster core composition as [Mo₆(µ₃-S)(µ₃-Cl)₇(S^tBu)₆]^3-. The analysis of the temperature factors of the atoms in the µ₃-positions leads us to the conclusion that two positions are occupied with Cl atoms only, while the remaining six positions are statistically occupied with Cl and S atoms in a 1:5 ratio (Fig. 1). The presence of one S atom in the cluster core has no noticeable effect on its geometry (Schoonover et al., 1996; Szczepura et al., 2008).

The structure contains two disordered lattice water molecules. One is located on a threefold rotation axis, the other is located in a general position. Both have an occupancy of 0.25 and are disordered over a site with symmetry 32. These two water molecules have an O ··· O distance of 2.706 (8) Å, pointing to hydrogen-bonding interactions. The water molecules are localized in cavities formed by the Bu₄N⁺ cations and ^tBuS groups. The water incorporated in the structure most likely originated from the starting material (Bu₄N)₂[Mo₆(µ₃-Cl)₈Cl₆]^.nH₂O.

The centres of the metal clusters are arranged in a cubic close packing along [001] as stacking direction (Fig. 2).

Related literature top

For a review of octahedral halogen-bridged metal clusters, see: Prokopuk & Shryver (1998). For synthesis and structures of related halogen/chalcogen clusters, see: Abramov et al. (2009); Ebihara et al. (1988); Ebihara, Imai et al. (1995); Ebihara, Toriumi et al. (1995); Michel & McCarley (1982); Nocera & Gray (1984). For synthesis and structures of related clusters with sulfur-substituted halogen atoms, see: Schoonover et al. (1996); Szczepura et al. (2008).

Experimental top

A mixture of 128.8 mg (0.083 mmol) (Bu₄N)₂[Mo₆Cl₁₄] and 154.8 mg (1.38 mmol) NaS^tBu (1:16.7 molar ratio) in 15 ml CH₃CN was refluxed for 5 days. The resulting brown solution was filtered to remove the white residue and left standing at 278 K. After several weeks almost black crystals were formed. The largest positive and negative residual electron densities are located 0.73 Å from atom OW3 and 0.58 Å from atom S2, respectively.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006) and POV-RAY (Persistence of Vision, 2004); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of [Mo₆(µ₃-S)(µ₃-Cl)₇(S^tBu)₆]^3- anion. Displacement ellipsoids are plotted at the 50% probability level.
	Fig. 2. Packing of the structure viewed along c axis. O and H atoms are omitted for clarity.

Tris(tetrabutylammonium) hexakis(tert-butanethiolato-κS)hepta-µ₃- chlorido-µ₃-sulfido-hexamolybdate dihydrate top

Crystal data top

(C₁₆H₃₆N)₃[Mo₆(C₄H₉S)₆Cl₇S]·2H₂O	D_x = 1.345 Mg m⁻³
M_r = 2154.29	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 9844 reflections
Hall symbol: -R 3 2"c	θ = 2.5–28.3°
a = 18.7481 (5) Å	µ = 1.04 mm⁻¹
c = 52.4233 (12) Å	T = 150 K
V = 15957.7 (7) Å³	Prism, brown
Z = 6	0.42 × 0.35 × 0.23 mm
F(000) = 6708

Data collection top

Bruker–Nonius X8 APEX CCD diffractometer	3637 independent reflections
Radiation source: fine-focus sealed tube	3092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 25 pixels mm^-1	θ_max = 26.4°, θ_min = 2.2°
ϕ scans	h = −23→23
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −23→22
T_min = 0.670, T_max = 0.797	l = −65→55
36925 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0654P)² + 69.7786P] where P = (F_o² + 2F_c²)/3
3637 reflections	(Δ/σ)_max < 0.001
161 parameters	Δρ_max = 1.16 e Å⁻³
12 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

(C₁₆H₃₆N)₃[Mo₆(C₄H₉S)₆Cl₇S]·2H₂O	Z = 6
M_r = 2154.29	Mo Kα radiation
Trigonal, R3c	µ = 1.04 mm⁻¹
a = 18.7481 (5) Å	T = 150 K
c = 52.4233 (12) Å	0.42 × 0.35 × 0.23 mm
V = 15957.7 (7) Å³

Data collection top

Bruker–Nonius X8 APEX CCD diffractometer	3637 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3092 reflections with I > 2σ(I)
T_min = 0.670, T_max = 0.797	R_int = 0.034
36925 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	12 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0654P)² + 69.7786P] where P = (F_o² + 2F_c²)/3
3637 reflections	Δρ_max = 1.16 e Å⁻³
161 parameters	Δρ_min = −0.76 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Hydrogen atoms of water molecules are not located. One of water molecules is disodered by two positions. Hydrogen atoms of cation and anion are placed geometrically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	0.093280 (16)	0.039723 (17)	0.020197 (5)	0.02512 (13)
Cl1	0.0000	0.0000	0.05819 (2)	0.0298 (3)
Cl2	0.07472 (5)	−0.10085 (5)	0.019692 (16)	0.0374 (2)	0.8333333
S1	0.21632 (6)	0.09894 (7)	0.049357 (18)	0.0458 (3)
S2	0.07472 (5)	−0.10085 (5)	0.019692 (16)	0.0374 (2)	0.1666667
O2W	0.5911 (10)	0.3102 (13)	0.0925 (4)	0.103 (6)	0.25
N1	0.2617 (3)	0.3333	0.0833	0.0555 (12)
C1	0.3076 (2)	0.0927 (3)	0.03926 (8)	0.0478 (9)
C2	0.3649 (4)	0.1194 (6)	0.06188 (11)	0.107 (3)
H2A	0.4128	0.1137	0.0578	0.161*
H2B	0.3359	0.0848	0.0766	0.161*
H2C	0.3831	0.1771	0.0659	0.161*
C3	0.2844 (4)	0.0089 (4)	0.02944 (17)	0.111 (3)
H3A	0.2454	−0.0054	0.0153	0.167*
H3B	0.2587	−0.0316	0.0432	0.167*
H3C	0.3339	0.0089	0.0234	0.167*
C4	0.3539 (4)	0.1528 (5)	0.01793 (13)	0.099 (2)
H4A	0.3731	0.2091	0.0238	0.148*
H4B	0.3172	0.1408	0.0033	0.148*
H4C	0.4013	0.1473	0.0129	0.148*
C11	0.3094 (3)	0.3354 (3)	0.10717 (8)	0.0559 (11)
H11A	0.3620	0.3883	0.1075	0.067*
H11B	0.2773	0.3342	0.1223	0.067*
C12	0.3281 (3)	0.2659 (3)	0.10940 (9)	0.0669 (13)
H12A	0.2761	0.2126	0.1078	0.080*
H12B	0.3645	0.2697	0.0952	0.080*
C13	0.3688 (4)	0.2676 (3)	0.13419 (10)	0.0809 (16)
H13A	0.3314	0.2620	0.1484	0.097*
H13B	0.4195	0.3218	0.1360	0.097*
C14	0.3909 (4)	0.2012 (4)	0.13669 (13)	0.0886 (18)
H14A	0.3405	0.1473	0.1369	0.133*
H14B	0.4214	0.2090	0.1526	0.133*
H14C	0.4252	0.2040	0.1222	0.133*
C21	0.2550 (3)	0.4108 (3)	0.08358 (10)	0.0649 (13)
H21A	0.3108	0.4587	0.0862	0.078*
H21B	0.2212	0.4081	0.0984	0.078*
C22	0.2179 (5)	0.4266 (4)	0.05962 (15)	0.107 (3)
H22A	0.2472	0.4229	0.0444	0.128*
H22B	0.1595	0.3828	0.0582	0.128*
C23	0.2222 (4)	0.5059 (4)	0.05953 (12)	0.0854 (17)
H23A	0.2808	0.5494	0.0606	0.102*
H23B	0.1942	0.5099	0.0750	0.102*
C24	0.1854 (6)	0.5224 (5)	0.03716 (18)	0.136 (4)
H24A	0.2026	0.5059	0.0216	0.204*
H24B	0.2039	0.5814	0.0364	0.204*
H24C	0.1252	0.4910	0.0386	0.204*
O1W	0.6667	0.3333	0.0468 (7)	0.095 (8)	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.02590 (17)	0.02668 (17)	0.02253 (19)	0.01297 (12)	−0.00049 (9)	−0.00092 (9)
Cl1	0.0327 (4)	0.0327 (4)	0.0241 (6)	0.0163 (2)	0.000	0.000
Cl2	0.0400 (4)	0.0387 (4)	0.0356 (4)	0.0212 (4)	−0.0011 (3)	0.0002 (3)
S1	0.0345 (5)	0.0652 (6)	0.0409 (5)	0.0273 (4)	−0.0101 (4)	−0.0199 (4)
S2	0.0400 (4)	0.0387 (4)	0.0356 (4)	0.0212 (4)	−0.0011 (3)	0.0002 (3)
O2W	0.049 (7)	0.116 (10)	0.122 (10)	0.024 (6)	0.007 (6)	0.007 (7)
N1	0.060 (2)	0.051 (3)	0.052 (3)	0.0254 (14)	−0.0121 (11)	−0.024 (2)
C1	0.0364 (19)	0.054 (2)	0.057 (2)	0.0256 (18)	−0.0009 (17)	−0.0042 (18)
C2	0.061 (3)	0.210 (8)	0.076 (4)	0.086 (5)	−0.021 (3)	−0.020 (4)
C3	0.061 (3)	0.066 (4)	0.219 (8)	0.040 (3)	0.019 (4)	−0.011 (4)
C4	0.055 (3)	0.126 (6)	0.100 (5)	0.034 (4)	0.019 (3)	0.031 (4)
C11	0.062 (3)	0.056 (3)	0.044 (2)	0.024 (2)	−0.0055 (19)	−0.0146 (18)
C12	0.082 (3)	0.063 (3)	0.058 (3)	0.039 (3)	−0.011 (2)	−0.015 (2)
C13	0.110 (5)	0.063 (3)	0.063 (3)	0.038 (3)	−0.013 (3)	−0.002 (2)
C14	0.100 (5)	0.088 (4)	0.082 (4)	0.050 (4)	−0.012 (3)	0.009 (3)
C21	0.061 (3)	0.057 (3)	0.075 (3)	0.028 (2)	−0.019 (2)	−0.033 (2)
C22	0.131 (6)	0.086 (4)	0.122 (5)	0.070 (4)	−0.078 (5)	−0.058 (4)
C23	0.086 (4)	0.081 (4)	0.094 (4)	0.045 (3)	−0.018 (3)	−0.026 (3)
C24	0.157 (8)	0.091 (5)	0.181 (8)	0.078 (5)	−0.083 (7)	−0.039 (5)
O1W	0.086 (8)	0.086 (8)	0.113 (12)	0.043 (4)	0.000	0.000

Geometric parameters (Å, º) top

Mo1—Mo1ⁱ	2.6067 (4)	C3—H3C	0.9800
Mo1—Mo1ⁱⁱ	2.6067 (4)	C4—H4A	0.9800
Mo1—Mo1ⁱⁱⁱ	2.6328 (5)	C4—H4B	0.9800
Mo1—Mo1^iv	2.6328 (5)	C4—H4C	0.9800
Mo1—S1	2.5158 (9)	C11—C12	1.515 (7)
Mo1—S2^iv	2.4792 (9)	C11—H11A	0.9900
Mo1—S2ⁱⁱ	2.4842 (9)	C11—H11B	0.9900
Mo1—Cl1	2.5054 (10)	C12—C13	1.500 (7)
Mo1—Cl2	2.4801 (9)	C12—H12A	0.9900
Mo1—Cl2^iv	2.4792 (9)	C12—H12B	0.9900
Mo1—Cl2ⁱⁱ	2.4842 (9)	C13—C14	1.501 (8)
Cl1—Mo1ⁱⁱⁱ	2.5054 (10)	C13—H13A	0.9900
Cl1—Mo1^iv	2.5054 (10)	C13—H13B	0.9900
Cl2—Mo1ⁱⁱⁱ	2.4792 (9)	C14—H14A	0.9800
Cl2—Mo1ⁱ	2.4842 (9)	C14—H14B	0.9800
S1—C1	1.849 (4)	C14—H14C	0.9800
O2W—O2W^v	1.22 (4)	C21—C22	1.535 (8)
N1—C21^v	1.520 (5)	C21—H21A	0.9900
N1—C21	1.520 (5)	C21—H21B	0.9900
N1—C11^v	1.525 (5)	C22—C23	1.448 (8)
N1—C11	1.525 (5)	C22—H22A	0.9900
C1—C3	1.497 (7)	C22—H22B	0.9900
C1—C2	1.508 (6)	C23—C24	1.470 (9)
C1—C4	1.515 (7)	C23—H23A	0.9900
C2—H2A	0.9800	C23—H23B	0.9900
C2—H2B	0.9800	C24—H24A	0.9800
C2—H2C	0.9800	C24—H24B	0.9800
C3—H3A	0.9800	C24—H24C	0.9800
C3—H3B	0.9800

S2^iv—Mo1—Cl2^iv	0.00 (5)	C2—C1—C4	106.6 (5)
S2^iv—Mo1—Cl2	175.69 (3)	C3—C1—S1	111.9 (3)
Cl2^iv—Mo1—Cl2	175.69 (3)	C2—C1—S1	106.4 (3)
S2^iv—Mo1—S2ⁱⁱ	90.61 (2)	C4—C1—S1	111.6 (4)
Cl2^iv—Mo1—S2ⁱⁱ	90.61 (2)	C1—C2—H2A	109.5
Cl2—Mo1—S2ⁱⁱ	90.59 (2)	C1—C2—H2B	109.5
S2^iv—Mo1—Cl2ⁱⁱ	90.61 (2)	H2A—C2—H2B	109.5
Cl2^iv—Mo1—Cl2ⁱⁱ	90.61 (2)	C1—C2—H2C	109.5
Cl2—Mo1—Cl2ⁱⁱ	90.59 (2)	H2A—C2—H2C	109.5
S2ⁱⁱ—Mo1—Cl2ⁱⁱ	0.00 (5)	H2B—C2—H2C	109.5
S2^iv—Mo1—Cl1	89.24 (2)	C1—C3—H3A	109.5
Cl2^iv—Mo1—Cl1	89.24 (2)	C1—C3—H3B	109.5
Cl2—Mo1—Cl1	89.22 (2)	H3A—C3—H3B	109.5
S2ⁱⁱ—Mo1—Cl1	175.32 (3)	C1—C3—H3C	109.5
Cl2ⁱⁱ—Mo1—Cl1	175.32 (3)	H3A—C3—H3C	109.5
S2^iv—Mo1—S1	89.10 (3)	H3B—C3—H3C	109.5
Cl2^iv—Mo1—S1	89.10 (3)	C1—C4—H4A	109.5
Cl2—Mo1—S1	94.93 (3)	C1—C4—H4B	109.5
S2ⁱⁱ—Mo1—S1	94.79 (3)	H4A—C4—H4B	109.5
Cl2ⁱⁱ—Mo1—S1	94.79 (3)	C1—C4—H4C	109.5
Cl1—Mo1—S1	89.88 (3)	H4A—C4—H4C	109.5
S2^iv—Mo1—Mo1ⁱ	119.05 (2)	H4B—C4—H4C	109.5
Cl2^iv—Mo1—Mo1ⁱ	119.05 (2)	C12—C11—N1	115.2 (3)
Cl2—Mo1—Mo1ⁱ	58.40 (2)	C12—C11—H11A	108.5
S2ⁱⁱ—Mo1—Mo1ⁱ	58.22 (2)	N1—C11—H11A	108.5
Cl2ⁱⁱ—Mo1—Mo1ⁱ	58.22 (2)	C12—C11—H11B	108.5
Cl1—Mo1—Mo1ⁱ	117.960 (18)	N1—C11—H11B	108.5
S1—Mo1—Mo1ⁱ	138.62 (2)	H11A—C11—H11B	107.5
S2^iv—Mo1—Mo1ⁱⁱ	58.41 (2)	C13—C12—C11	112.5 (4)
Cl2^iv—Mo1—Mo1ⁱⁱ	58.41 (2)	C13—C12—H12A	109.1
Cl2—Mo1—Mo1ⁱⁱ	119.04 (2)	C11—C12—H12A	109.1
S2ⁱⁱ—Mo1—Mo1ⁱⁱ	58.25 (2)	C13—C12—H12B	109.1
Cl2ⁱⁱ—Mo1—Mo1ⁱⁱ	58.25 (2)	C11—C12—H12B	109.1
Cl1—Mo1—Mo1ⁱⁱ	117.960 (17)	H12A—C12—H12B	107.8
S1—Mo1—Mo1ⁱⁱ	134.36 (3)	C12—C13—C14	114.0 (5)
Mo1ⁱ—Mo1—Mo1ⁱⁱ	60.665 (13)	C12—C13—H13A	108.8
S2^iv—Mo1—Mo1ⁱⁱⁱ	117.95 (2)	C14—C13—H13A	108.8
Cl2^iv—Mo1—Mo1ⁱⁱⁱ	117.95 (2)	C12—C13—H13B	108.8
Cl2—Mo1—Mo1ⁱⁱⁱ	57.92 (2)	C14—C13—H13B	108.8
S2ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	117.86 (2)	H13A—C13—H13B	107.7
Cl2ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	117.86 (2)	C13—C14—H14A	109.5
Cl1—Mo1—Mo1ⁱⁱⁱ	58.302 (15)	C13—C14—H14B	109.5
S1—Mo1—Mo1ⁱⁱⁱ	135.38 (3)	H14A—C14—H14B	109.5
Mo1ⁱ—Mo1—Mo1ⁱⁱⁱ	59.667 (7)	C13—C14—H14C	109.5
Mo1ⁱⁱ—Mo1—Mo1ⁱⁱⁱ	90.0	H14A—C14—H14C	109.5
S2^iv—Mo1—Mo1^iv	57.95 (2)	H14B—C14—H14C	109.5
Cl2^iv—Mo1—Mo1^iv	57.95 (2)	N1—C21—C22	116.1 (4)
Cl2—Mo1—Mo1^iv	117.91 (2)	N1—C21—H21A	108.3
S2ⁱⁱ—Mo1—Mo1^iv	117.89 (2)	C22—C21—H21A	108.3
Cl2ⁱⁱ—Mo1—Mo1^iv	117.89 (2)	N1—C21—H21B	108.3
Cl1—Mo1—Mo1^iv	58.302 (15)	C22—C21—H21B	108.3
S1—Mo1—Mo1^iv	131.38 (2)	H21A—C21—H21B	107.4
Mo1ⁱ—Mo1—Mo1^iv	90.0	C23—C22—C21	113.7 (5)
Mo1ⁱⁱ—Mo1—Mo1^iv	59.667 (7)	C23—C22—H22A	108.8
Mo1ⁱⁱⁱ—Mo1—Mo1^iv	60.0	C21—C22—H22A	108.8
Mo1ⁱⁱⁱ—Cl1—Mo1^iv	63.40 (3)	C23—C22—H22B	108.8
Mo1ⁱⁱⁱ—Cl1—Mo1	63.40 (3)	C21—C22—H22B	108.8
Mo1^iv—Cl1—Mo1	63.40 (3)	H22A—C22—H22B	107.7
Mo1ⁱⁱⁱ—Cl2—Mo1	64.13 (2)	C22—C23—C24	115.3 (5)
Mo1ⁱⁱⁱ—Cl2—Mo1ⁱ	63.36 (2)	C22—C23—H23A	108.4
Mo1—Cl2—Mo1ⁱ	63.35 (2)	C24—C23—H23A	108.4
C1—S1—Mo1	118.11 (13)	C22—C23—H23B	108.4
C21^v—N1—C21	111.8 (5)	C24—C23—H23B	108.4
C21^v—N1—C11^v	107.2 (2)	H23A—C23—H23B	107.5
C21—N1—C11^v	110.3 (3)	C23—C24—H24A	109.5
C21^v—N1—C11	110.3 (3)	C23—C24—H24B	109.5
C21—N1—C11	107.2 (2)	H24A—C24—H24B	109.5
C11^v—N1—C11	110.1 (5)	C23—C24—H24C	109.5
C3—C1—C2	113.8 (5)	H24A—C24—H24C	109.5
C3—C1—C4	106.5 (5)	H24B—C24—H24C	109.5

Symmetry codes: (i) y, −x+y, −z; (ii) x−y, x, −z; (iii) −x+y, −x, z; (iv) −y, x−y, z; (v) x−y+1/3, −y+2/3, −z+1/6.

Experimental details

Crystal data
Chemical formula	(C₁₆H₃₆N)₃[Mo₆(C₄H₉S)₆Cl₇S]·2H₂O
M_r	2154.29
Crystal system, space group	Trigonal, R3c
Temperature (K)	150
a, c (Å)	18.7481 (5), 52.4233 (12)
V (Å³)	15957.7 (7)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.42 × 0.35 × 0.23

Data collection
Diffractometer	Bruker–Nonius X8 APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.670, 0.797
No. of measured, independent and observed [I > 2σ(I)] reflections	36925, 3637, 3092
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.125, 1.14
No. of reflections	3637
No. of parameters	161
No. of restraints	12
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0654P)² + 69.7786P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.16, −0.76

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006) and POV-RAY (Persistence of Vision, 2004), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mo1—Mo1ⁱ	2.6067 (4)	Mo1—Cl1	2.5054 (10)
Mo1—Mo1ⁱⁱ	2.6328 (5)	Mo1—Cl2	2.4801 (9)
Mo1—S1	2.5158 (9)	Mo1—Cl2ⁱⁱⁱ	2.4792 (9)
Mo1—S2ⁱⁱⁱ	2.4792 (9)	Mo1—Cl2^iv	2.4842 (9)
Mo1—S2^iv	2.4842 (9)

Symmetry codes: (i) y, −x+y, −z; (ii) −x+y, −x, z; (iii) −y, x−y, z; (iv) x−y, x, −z.

Acknowledgements

The work was supported by RFBR (grants 09–03-38245a and 10–03-38245a) and State Contract GK-02.740.11.0628. The authors are grateful to Dr Cristian Vicent (Universitat Jaume I, Castello, Spain) for ES-MS data.

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