Tris(tetra-butyl-ammonium) hexa-kis-(tert-butane-thiol-ato-κS)hepta-μ(3)-chlorido-μ(3)-sulfido-hexa-molybdate dihydrate.

The octa-hedral cluster core of the anion in the structure of the title compound, (C(16)H(36)N)(3)[Mo(6)(C(4)H(9)S)(6)(μ(3)-Cl)(7)(μ(3)-S)]·2H(2)O, has -3 site symmetry. Two μ(3)-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 tetra-butyl-ammonium cation is located on a site with 2 symmetry. The structure contains also two disordered solvent water mol-ecules, 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 mol-ecules are localized in cavities formed by the tetra-butyl-ammonium cations and the tert-butane-thiol-ate 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 = 2154.29

Trigonal,

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[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.125

S = 1.14

3637 reflections

161 parameters

12 restraints

H-atom parameters constrained

Δρmax = 1.16 e Å−3

Δρmin = −0.76 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007416/wm2589sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C16H36N)3[Mo6(C4H9S)6Cl7S]·2H2O	Dx = 1.345 Mg m−3
Mr = 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

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

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(Fo2) + (0.0654P)2 + 69.7786P] where P = (Fo2 + 2Fc2)/3
3637 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 1.16 e Å−3
12 restraints	Δρmin = −0.76 e Å−3

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.

	x	y	z	Uiso*/Ueq	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

	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

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—Mo1iv	2.6328 (5)	C4—H4C	0.9800
Mo1—S1	2.5158 (9)	C11—C12	1.515 (7)
Mo1—S2iv	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—Cl2iv	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—Mo1iv	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—O2Wv	1.22 (4)	C21—C22	1.535 (8)
N1—C21v	1.520 (5)	C21—H21A	0.9900
N1—C21	1.520 (5)	C21—H21B	0.9900
N1—C11v	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
S2iv—Mo1—Cl2iv	0.00 (5)	C2—C1—C4	106.6 (5)
S2iv—Mo1—Cl2	175.69 (3)	C3—C1—S1	111.9 (3)
Cl2iv—Mo1—Cl2	175.69 (3)	C2—C1—S1	106.4 (3)
S2iv—Mo1—S2ii	90.61 (2)	C4—C1—S1	111.6 (4)
Cl2iv—Mo1—S2ii	90.61 (2)	C1—C2—H2A	109.5
Cl2—Mo1—S2ii	90.59 (2)	C1—C2—H2B	109.5
S2iv—Mo1—Cl2ii	90.61 (2)	H2A—C2—H2B	109.5
Cl2iv—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
S2iv—Mo1—Cl1	89.24 (2)	C1—C3—H3A	109.5
Cl2iv—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
S2iv—Mo1—S1	89.10 (3)	H3B—C3—H3C	109.5
Cl2iv—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
S2iv—Mo1—Mo1i	119.05 (2)	H4B—C4—H4C	109.5
Cl2iv—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
S2iv—Mo1—Mo1ii	58.41 (2)	C13—C12—C11	112.5 (4)
Cl2iv—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
S2iv—Mo1—Mo1iii	117.95 (2)	C14—C13—H13A	108.8
Cl2iv—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
S2iv—Mo1—Mo1iv	57.95 (2)	H14B—C14—H14C	109.5
Cl2iv—Mo1—Mo1iv	57.95 (2)	N1—C21—C22	116.1 (4)
Cl2—Mo1—Mo1iv	117.91 (2)	N1—C21—H21A	108.3
S2ii—Mo1—Mo1iv	117.89 (2)	C22—C21—H21A	108.3
Cl2ii—Mo1—Mo1iv	117.89 (2)	N1—C21—H21B	108.3
Cl1—Mo1—Mo1iv	58.302 (15)	C22—C21—H21B	108.3
S1—Mo1—Mo1iv	131.38 (2)	H21A—C21—H21B	107.4
Mo1i—Mo1—Mo1iv	90.0	C23—C22—C21	113.7 (5)
Mo1ii—Mo1—Mo1iv	59.667 (7)	C23—C22—H22A	108.8
Mo1iii—Mo1—Mo1iv	60.0	C21—C22—H22A	108.8
Mo1iii—Cl1—Mo1iv	63.40 (3)	C23—C22—H22B	108.8
Mo1iii—Cl1—Mo1	63.40 (3)	C21—C22—H22B	108.8
Mo1iv—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
C21v—N1—C21	111.8 (5)	C24—C23—H23B	108.4
C21v—N1—C11v	107.2 (2)	H23A—C23—H23B	107.5
C21—N1—C11v	110.3 (3)	C23—C24—H24A	109.5
C21v—N1—C11	110.3 (3)	C23—C24—H24B	109.5
C21—N1—C11	107.2 (2)	H24A—C24—H24B	109.5
C11v—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

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—S2iv	2.4842 (9)
Mo1—Cl1	2.5054 (10)
Mo1—Cl2	2.4801 (9)
Mo1—Cl2iii	2.4792 (9)
Mo1—Cl2iv	2.4842 (9)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .