Hexa­kis­(dimethyl sulfoxide-κO)calcium μ6-oxido-dodeca­kis-μ2-oxido-hexa­oxido­hexa­tungstate(VI)

Zhang, J.

doi:10.1107/S1600536812018338

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m702

doi:10.1107/S1600536812018338

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Hexakis(dimethyl sulfoxide-κO)calcium μ₆-oxido-dodecakis-μ₂-oxido-hexaoxidohexatungstate(VI)

Jinfang Zhang ^a ^*

^aMolecular Materials Research Center, Scientific Research Academy, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: zjf260@ujs.edu.cn

(Received 13 April 2012; accepted 24 April 2012; online 28 April 2012)

In the title compound, [Ca(C₂H₆OS)₆][W₆O₁₉], the cation and anion both have a crystallographically imposed centre of symmetry. The Ca^II atom in the cation is coordinated by six O atoms from six dimethyl sulfoxide ligands in a distorted octahedral geometry. The [W₆O₁₉]²⁻ isopolyanion possesses the well-known Lindqvist structure in which each W^VI atom is coordinated by four μ₂-O, one terminal O and one μ₆-O atom.

Related literature

For the in situ synthetic method, see: Xu et al. (2010 ); Ni et al. (2009 ).

Experimental

Crystal data

[Ca(C₂H₆OS)₆][W₆O₁₉]
M_r = 1915.95
Triclinic, $[P \overline 1]$
a = 8.1871 (16) Å
b = 11.352 (2) Å
c = 11.378 (2) Å
α = 84.53 (3)°
β = 73.15 (3)°
γ = 74.02 (3)°
V = 972.8 (3) Å³
Z = 1
Mo Kα radiation
μ = 18.20 mm⁻¹
T = 293 K
0.21 × 0.15 × 0.13 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.047, T_max = 0.094
8635 measured reflections
3507 independent reflections
3072 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.047
S = 0.98
3507 reflections
229 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −1.19 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018338/rz2743sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018338/rz2743Isup2.hkl

checkCIF report

Comment top

The in situ synthetic method has been widely applied to constructing new compounds (Xu et al., 2010, Ni et al., 2009). In the present paper, the in situ reaction between tetrathiotungstate and calcium nitrate in DMSO to form the title compound is reported. The (W₆O₁₉)^2- isopolyanion was achieved by the reaction between (WS₄)^2- and H₂O in DMSO solution.

In the cation of the title compound (Fig. 1), the Ca²⁺ ion is bonded by six O atoms from six DMSO ligands in a distorted octahedral coordination geometry. The (W₆O₁₉)^2- (Fig. 2) shows the usual cage-shaped Lindqvist structure, where each W atom is coordinated by four µ₂-O, one terminal O and one µ₆-O atoms. The W—O bond lengths involving the µ₆-O atoms [2.3255 (8)–2.3292 (6) Å] are obviously longer than those observed for the µ₂-O [1.905 (4)–1.934 (4) Å] and terminal [1.696 (4)–1.703 (4) Å] oxygen atoms.

Related literature top

For the in situ synthetic method, see: Xu et al. (2010); Ni et al. (2009).

Experimental top

Calcium nitrate (1 mmol) was added to a solution of [NH₄]₂WS₄ (1 mmol in 5 ml DMSO) with thorough stir for 30 minutes. After filtration, the orange filtrate was carefully laid on the surface with 8 ml i-PrOH. Colourless block crystals were obtained after about one month.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the cation in the title compound, with 30% probability displacement ellipsoids. H atoms have been omitted. Symmetry code: (i) -x, 1 - y, 1 - z.
	Fig. 2. The molecular structure of the anion in the title compound, with 30% probability displacement ellipsoids. Symmetry code: (i) 1 - x, -y, -z.

Hexakis(dimethyl sulfoxide-κO)calcium µ₆-oxido-dodecakis-µ₂-oxido-hexaoxidohexatungstate(VI) top

Crystal data top

[Ca(C₂H₆OS)₆][W₆O₁₉]	Z = 1
M_r = 1915.95	F(000) = 868
Triclinic, P1	D_x = 3.270 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1871 (16) Å	Cell parameters from 4353 reflections
b = 11.352 (2) Å	θ = 3.7–29.0°
c = 11.378 (2) Å	µ = 18.20 mm⁻¹
α = 84.53 (3)°	T = 293 K
β = 73.15 (3)°	Block, colourless
γ = 74.02 (3)°	0.21 × 0.15 × 0.13 mm
V = 972.8 (3) Å³

Data collection top

Rigaku Saturn724+ diffractometer	3507 independent reflections
Radiation source: fine-focus sealed tube	3072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 25.4°, θ_min = 3.7°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −9→9
T_min = 0.047, T_max = 0.094	k = −12→13
8635 measured reflections	l = −13→12

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.047	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0163P)²] where P = (F_o² + 2F_c²)/3
3507 reflections	(Δ/σ)_max = 0.001
229 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −1.19 e Å⁻³

Crystal data top

[Ca(C₂H₆OS)₆][W₆O₁₉]	γ = 74.02 (3)°
M_r = 1915.95	V = 972.8 (3) Å³
Triclinic, P1	Z = 1
a = 8.1871 (16) Å	Mo Kα radiation
b = 11.352 (2) Å	µ = 18.20 mm⁻¹
c = 11.378 (2) Å	T = 293 K
α = 84.53 (3)°	0.21 × 0.15 × 0.13 mm
β = 73.15 (3)°

Data collection top

Rigaku Saturn724+ diffractometer	3507 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	3072 reflections with I > 2σ(I)
T_min = 0.047, T_max = 0.094	R_int = 0.034
8635 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.047	H-atom parameters constrained
S = 0.98	Δρ_max = 1.05 e Å⁻³
3507 reflections	Δρ_min = −1.19 e Å⁻³
229 parameters

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.

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

	x	y	z	U_iso*/U_eq
Ca1	0.0000	0.5000	0.5000	0.0163 (4)
S1	−0.2595 (2)	0.38529 (14)	0.35230 (14)	0.0203 (3)
S2	0.2007 (2)	0.23054 (14)	0.63729 (14)	0.0206 (3)
S3	0.3557 (2)	0.47593 (14)	0.21704 (13)	0.0205 (4)
O1	−0.2315 (5)	0.4680 (4)	0.4393 (3)	0.0232 (10)
O2	0.0581 (5)	0.3034 (4)	0.5797 (4)	0.0250 (10)
O3	0.2119 (5)	0.4354 (4)	0.3150 (3)	0.0224 (10)
C1	−0.1301 (9)	0.4158 (6)	0.2049 (5)	0.0302 (16)
H1A	−0.1824	0.4963	0.1777	0.045*
H1B	−0.1247	0.3562	0.1485	0.045*
H1C	−0.0129	0.4115	0.2085	0.045*
C2	−0.1315 (9)	0.2352 (6)	0.3743 (6)	0.0293 (16)
H2A	−0.1852	0.2032	0.4529	0.044*
H2B	−0.0142	0.2379	0.3713	0.044*
H2C	−0.1259	0.1831	0.3107	0.044*
C3	0.1723 (8)	0.0790 (5)	0.6536 (6)	0.0251 (15)
H3A	0.0671	0.0769	0.7180	0.038*
H3B	0.2726	0.0233	0.6737	0.038*
H3C	0.1619	0.0553	0.5779	0.038*
C4	0.4000 (8)	0.2041 (6)	0.5156 (6)	0.0321 (17)
H4A	0.4348	0.2792	0.4944	0.048*
H4B	0.3812	0.1750	0.4453	0.048*
H4C	0.4913	0.1439	0.5415	0.048*
C5	0.2577 (9)	0.5451 (6)	0.0969 (5)	0.0299 (16)
H5A	0.2362	0.4830	0.0561	0.045*
H5B	0.3366	0.5856	0.0388	0.045*
H5C	0.1480	0.6039	0.1314	0.045*
C6	0.3767 (9)	0.6117 (6)	0.2698 (6)	0.0290 (16)
H6A	0.4292	0.5919	0.3368	0.044*
H6B	0.2619	0.6676	0.2970	0.044*
H6C	0.4502	0.6492	0.2041	0.044*
W1	0.29354 (3)	0.17964 (2)	−0.02810 (2)	0.01538 (7)
W2	0.34391 (3)	−0.00577 (2)	0.20593 (2)	0.01614 (8)
W3	0.66800 (3)	0.11373 (2)	0.04884 (2)	0.01671 (8)
O4	0.5000	0.0000	0.0000	0.0149 (12)
O5	0.4702 (5)	0.2359 (3)	0.0143 (3)	0.0159 (9)
O6	0.1471 (5)	0.3129 (4)	−0.0504 (4)	0.0237 (10)
O7	0.2105 (5)	0.1407 (4)	0.1419 (3)	0.0182 (9)
O8	0.5081 (5)	0.0881 (4)	0.2053 (3)	0.0161 (9)
O9	0.7883 (6)	0.1969 (4)	0.0863 (4)	0.0286 (11)
O10	0.2012 (5)	0.0534 (4)	−0.0611 (3)	0.0181 (9)
O11	0.4597 (5)	0.1488 (3)	−0.1889 (3)	0.0178 (9)
O12	0.2325 (5)	−0.0106 (4)	0.3573 (3)	0.0238 (10)
O13	0.2413 (5)	−0.0963 (4)	0.1266 (3)	0.0183 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0190 (9)	0.0153 (10)	0.0149 (8)	−0.0052 (8)	−0.0050 (7)	0.0023 (7)
S1	0.0193 (8)	0.0218 (9)	0.0217 (8)	−0.0076 (7)	−0.0067 (7)	0.0002 (7)
S2	0.0207 (8)	0.0197 (9)	0.0207 (8)	−0.0029 (7)	−0.0075 (7)	0.0012 (7)
S3	0.0203 (8)	0.0207 (9)	0.0183 (8)	−0.0051 (7)	−0.0027 (7)	0.0013 (7)
O1	0.025 (2)	0.025 (3)	0.020 (2)	−0.004 (2)	−0.0088 (19)	−0.0027 (19)
O2	0.020 (2)	0.020 (2)	0.035 (2)	−0.005 (2)	−0.011 (2)	0.009 (2)
O3	0.026 (2)	0.023 (3)	0.017 (2)	−0.010 (2)	0.0001 (19)	0.0023 (18)
C1	0.041 (4)	0.035 (4)	0.019 (3)	−0.018 (3)	−0.007 (3)	0.000 (3)
C2	0.037 (4)	0.022 (4)	0.030 (4)	−0.008 (3)	−0.012 (3)	0.003 (3)
C3	0.027 (4)	0.018 (4)	0.031 (4)	−0.006 (3)	−0.009 (3)	0.003 (3)
C4	0.016 (4)	0.044 (5)	0.032 (4)	−0.008 (3)	−0.003 (3)	0.009 (3)
C5	0.036 (4)	0.031 (4)	0.023 (4)	−0.010 (3)	−0.008 (3)	0.006 (3)
C6	0.033 (4)	0.032 (4)	0.025 (4)	−0.020 (3)	−0.003 (3)	0.003 (3)
W1	0.01630 (14)	0.01265 (14)	0.01563 (13)	−0.00101 (10)	−0.00495 (10)	0.00088 (10)
W2	0.01678 (14)	0.01716 (15)	0.01205 (13)	−0.00261 (11)	−0.00237 (10)	0.00101 (10)
W3	0.01879 (14)	0.01511 (15)	0.01880 (14)	−0.00643 (11)	−0.00742 (10)	0.00045 (10)
O4	0.013 (3)	0.015 (3)	0.014 (3)	−0.005 (2)	−0.001 (2)	0.006 (2)
O5	0.022 (2)	0.011 (2)	0.014 (2)	−0.0026 (18)	−0.0071 (18)	0.0002 (17)
O6	0.025 (2)	0.019 (2)	0.023 (2)	−0.001 (2)	−0.0060 (19)	0.0046 (19)
O7	0.019 (2)	0.017 (2)	0.017 (2)	−0.0013 (18)	−0.0047 (18)	−0.0019 (18)
O8	0.021 (2)	0.017 (2)	0.0113 (19)	−0.0040 (18)	−0.0053 (17)	−0.0049 (17)
O9	0.031 (3)	0.027 (3)	0.037 (3)	−0.015 (2)	−0.015 (2)	−0.004 (2)
O10	0.019 (2)	0.018 (2)	0.020 (2)	−0.0067 (18)	−0.0061 (18)	−0.0017 (18)
O11	0.022 (2)	0.015 (2)	0.015 (2)	−0.0046 (19)	−0.0057 (18)	0.0052 (17)
O12	0.028 (3)	0.027 (3)	0.011 (2)	−0.004 (2)	−0.0014 (19)	0.0024 (18)
O13	0.016 (2)	0.021 (2)	0.019 (2)	−0.0080 (19)	−0.0049 (18)	0.0077 (18)

Geometric parameters (Å, º) top

S1—O1	1.530 (4)	C6—H6C	0.9600
S1—C1	1.765 (6)	W1—O6	1.701 (4)
S1—C2	1.776 (6)	W1—O10	1.905 (4)
S2—O2	1.512 (4)	W1—O7	1.907 (4)
S2—C4	1.780 (6)	W1—O5	1.924 (4)
S2—C3	1.784 (6)	W1—O11	1.934 (4)
S3—O3	1.509 (4)	W1—O4	2.3258 (9)
S3—C6	1.775 (6)	W2—O12	1.703 (4)
S3—C5	1.792 (6)	W2—O13	1.916 (4)
C1—H1A	0.9600	W2—O11ⁱ	1.924 (4)
C1—H1B	0.9600	W2—O7	1.929 (4)
C1—H1C	0.9600	W2—O8	1.930 (4)
C2—H2A	0.9600	W2—O4	2.3255 (8)
C2—H2B	0.9600	W3—O9	1.696 (4)
C2—H2C	0.9600	W3—O10ⁱ	1.919 (4)
C3—H3A	0.9600	W3—O13ⁱ	1.926 (4)
C3—H3B	0.9600	W3—O5	1.931 (4)
C3—H3C	0.9600	W3—O8	1.931 (4)
C4—H4A	0.9600	W3—O4	2.3292 (6)
C4—H4B	0.9600	O4—W2ⁱ	2.3255 (8)
C4—H4C	0.9600	O4—W1ⁱ	2.3258 (9)
C5—H5A	0.9600	O4—W3ⁱ	2.3292 (6)
C5—H5B	0.9600	O10—W3ⁱ	1.919 (4)
C5—H5C	0.9600	O11—W2ⁱ	1.924 (4)
C6—H6A	0.9600	O13—W3ⁱ	1.926 (4)
C6—H6B	0.9600

O1—S1—C1	105.5 (3)	O10—W1—O4	76.19 (12)
O1—S1—C2	106.5 (3)	O7—W1—O4	76.43 (12)
C1—S1—C2	98.3 (3)	O5—W1—O4	76.06 (11)
O2—S2—C4	105.3 (3)	O11—W1—O4	76.15 (12)
O2—S2—C3	104.4 (3)	O12—W2—O13	104.30 (18)
C4—S2—C3	98.5 (3)	O12—W2—O11ⁱ	103.04 (18)
O3—S3—C6	106.8 (3)	O13—W2—O11ⁱ	86.91 (16)
O3—S3—C5	106.0 (3)	O12—W2—O7	104.58 (18)
C6—S3—C5	97.5 (3)	O13—W2—O7	87.18 (16)
S1—C1—H1A	109.5	O11ⁱ—W2—O7	152.37 (16)
S1—C1—H1B	109.5	O12—W2—O8	102.96 (18)
H1A—C1—H1B	109.5	O13—W2—O8	152.74 (15)
S1—C1—H1C	109.5	O11ⁱ—W2—O8	86.82 (16)
H1A—C1—H1C	109.5	O7—W2—O8	86.18 (17)
H1B—C1—H1C	109.5	O12—W2—O4	179.15 (14)
S1—C2—H2A	109.5	O13—W2—O4	76.27 (11)
S1—C2—H2B	109.5	O11ⁱ—W2—O4	76.33 (11)
H2A—C2—H2B	109.5	O7—W2—O4	76.04 (11)
S1—C2—H2C	109.5	O8—W2—O4	76.47 (11)
H2A—C2—H2C	109.5	O9—W3—O10ⁱ	104.34 (19)
H2B—C2—H2C	109.5	O9—W3—O13ⁱ	104.75 (19)
S2—C3—H3A	109.5	O10ⁱ—W3—O13ⁱ	86.68 (17)
S2—C3—H3B	109.5	O9—W3—O5	103.97 (19)
H3A—C3—H3B	109.5	O10ⁱ—W3—O5	151.69 (16)
S2—C3—H3C	109.5	O13ⁱ—W3—O5	85.75 (16)
H3A—C3—H3C	109.5	O9—W3—O8	102.89 (18)
H3B—C3—H3C	109.5	O10ⁱ—W3—O8	87.37 (16)
S2—C4—H4A	109.5	O13ⁱ—W3—O8	152.35 (16)
S2—C4—H4B	109.5	O5—W3—O8	86.80 (16)
H4A—C4—H4B	109.5	O9—W3—O4	179.23 (15)
S2—C4—H4C	109.5	O10ⁱ—W3—O4	75.84 (11)
H4A—C4—H4C	109.5	O13ⁱ—W3—O4	76.00 (11)
H4B—C4—H4C	109.5	O5—W3—O4	75.85 (11)
S3—C5—H5A	109.5	O8—W3—O4	76.36 (11)
S3—C5—H5B	109.5	W2—O4—W2ⁱ	180.000 (15)
H5A—C5—H5B	109.5	W2—O4—W1ⁱ	90.19 (4)
S3—C5—H5C	109.5	W2ⁱ—O4—W1ⁱ	89.81 (4)
H5A—C5—H5C	109.5	W2—O4—W1	89.81 (4)
H5B—C5—H5C	109.5	W2ⁱ—O4—W1	90.19 (4)
S3—C6—H6A	109.5	W1ⁱ—O4—W1	180.000 (18)
S3—C6—H6B	109.5	W2—O4—W3	90.07 (3)
H6A—C6—H6B	109.5	W2ⁱ—O4—W3	89.93 (3)
S3—C6—H6C	109.5	W1ⁱ—O4—W3	89.690 (19)
H6A—C6—H6C	109.5	W1—O4—W3	90.310 (19)
H6B—C6—H6C	109.5	W2—O4—W3ⁱ	89.93 (3)
O6—W1—O10	105.04 (19)	W2ⁱ—O4—W3ⁱ	90.07 (3)
O6—W1—O7	104.53 (18)	W1ⁱ—O4—W3ⁱ	90.310 (19)
O10—W1—O7	87.11 (16)	W1—O4—W3ⁱ	89.690 (19)
O6—W1—O5	102.69 (18)	W3—O4—W3ⁱ	180.000 (12)
O10—W1—O5	152.24 (17)	W1—O5—W3	117.76 (19)
O7—W1—O5	87.11 (16)	W1—O7—W2	117.72 (19)
O6—W1—O11	102.88 (18)	W2—O8—W3	117.10 (18)
O10—W1—O11	86.69 (16)	W1—O10—W3ⁱ	118.3 (2)
O7—W1—O11	152.57 (17)	W2ⁱ—O11—W1	117.33 (19)
O5—W1—O11	86.06 (16)	W2—O13—W3ⁱ	117.79 (18)
O6—W1—O4	178.43 (14)

O13—W2—O4—W1ⁱ	−89.97 (12)	O8—W3—O4—W1	89.34 (13)
O11ⁱ—W2—O4—W1ⁱ	0.16 (12)	O6—W1—O5—W3	179.93 (19)
O7—W2—O4—W1ⁱ	179.54 (12)	O10—W1—O5—W3	−2.5 (4)
O8—W2—O4—W1ⁱ	90.15 (12)	O7—W1—O5—W3	75.7 (2)
O13—W2—O4—W1	90.03 (12)	O11—W1—O5—W3	−77.7 (2)
O11ⁱ—W2—O4—W1	−179.84 (12)	O4—W1—O5—W3	−1.05 (15)
O7—W2—O4—W1	−0.46 (12)	O9—W3—O5—W1	−178.2 (2)
O8—W2—O4—W1	−89.85 (12)	O10ⁱ—W3—O5—W1	2.7 (4)
O13—W2—O4—W3	−179.66 (12)	O13ⁱ—W3—O5—W1	77.7 (2)
O11ⁱ—W2—O4—W3	−89.53 (12)	O8—W3—O5—W1	−75.7 (2)
O7—W2—O4—W3	89.85 (12)	O4—W3—O5—W1	1.05 (15)
O8—W2—O4—W3	0.46 (12)	O6—W1—O7—W2	−179.4 (2)
O13—W2—O4—W3ⁱ	0.34 (12)	O10—W1—O7—W2	75.8 (2)
O11ⁱ—W2—O4—W3ⁱ	90.47 (12)	O5—W1—O7—W2	−77.0 (2)
O7—W2—O4—W3ⁱ	−90.15 (12)	O11—W1—O7—W2	−1.3 (5)
O8—W2—O4—W3ⁱ	−179.54 (12)	O4—W1—O7—W2	−0.64 (16)
O10—W1—O4—W2	−89.87 (12)	O12—W2—O7—W1	−180.0 (2)
O7—W1—O4—W2	0.47 (12)	O13—W2—O7—W1	−75.9 (2)
O5—W1—O4—W2	90.83 (11)	O11ⁱ—W2—O7—W1	1.9 (5)
O11—W1—O4—W2	−179.84 (12)	O8—W2—O7—W1	77.6 (2)
O10—W1—O4—W2ⁱ	90.13 (12)	O4—W2—O7—W1	0.64 (16)
O7—W1—O4—W2ⁱ	−179.53 (12)	O12—W2—O8—W3	178.7 (2)
O5—W1—O4—W2ⁱ	−89.17 (11)	O13—W2—O8—W3	−0.9 (5)
O11—W1—O4—W2ⁱ	0.16 (12)	O11ⁱ—W2—O8—W3	76.1 (2)
O10—W1—O4—W3	−179.94 (11)	O7—W2—O8—W3	−77.2 (2)
O7—W1—O4—W3	−89.60 (12)	O4—W2—O8—W3	−0.63 (16)
O5—W1—O4—W3	0.77 (11)	O9—W3—O8—W2	−179.6 (2)
O11—W1—O4—W3	90.10 (12)	O10ⁱ—W3—O8—W2	−75.4 (2)
O10—W1—O4—W3ⁱ	0.06 (11)	O13ⁱ—W3—O8—W2	2.3 (5)
O7—W1—O4—W3ⁱ	90.40 (12)	O5—W3—O8—W2	76.8 (2)
O5—W1—O4—W3ⁱ	−179.23 (11)	O4—W3—O8—W2	0.63 (16)
O11—W1—O4—W3ⁱ	−89.90 (12)	O6—W1—O10—W3ⁱ	178.9 (2)
O10ⁱ—W3—O4—W2	90.26 (12)	O7—W1—O10—W3ⁱ	−76.8 (2)
O13ⁱ—W3—O4—W2	−179.67 (12)	O5—W1—O10—W3ⁱ	1.4 (5)
O5—W3—O4—W2	−90.57 (11)	O11—W1—O10—W3ⁱ	76.5 (2)
O8—W3—O4—W2	−0.46 (12)	O4—W1—O10—W3ⁱ	−0.09 (16)
O10ⁱ—W3—O4—W2ⁱ	−89.74 (12)	O6—W1—O11—W2ⁱ	178.5 (2)
O13ⁱ—W3—O4—W2ⁱ	0.33 (12)	O10—W1—O11—W2ⁱ	−76.8 (2)
O5—W3—O4—W2ⁱ	89.43 (11)	O7—W1—O11—W2ⁱ	0.4 (5)
O8—W3—O4—W2ⁱ	179.54 (12)	O5—W1—O11—W2ⁱ	76.4 (2)
O10ⁱ—W3—O4—W1ⁱ	0.06 (11)	O4—W1—O11—W2ⁱ	−0.22 (16)
O13ⁱ—W3—O4—W1ⁱ	90.14 (13)	O12—W2—O13—W3ⁱ	−179.8 (2)
O5—W3—O4—W1ⁱ	179.23 (11)	O11ⁱ—W2—O13—W3ⁱ	−77.1 (2)
O8—W3—O4—W1ⁱ	−90.66 (13)	O7—W2—O13—W3ⁱ	75.9 (2)
O10ⁱ—W3—O4—W1	−179.94 (11)	O8—W2—O13—W3ⁱ	−0.2 (5)
O13ⁱ—W3—O4—W1	−89.86 (13)	O4—W2—O13—W3ⁱ	−0.46 (16)
O5—W3—O4—W1	−0.77 (11)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Ca(C₂H₆OS)₆][W₆O₁₉]
M_r	1915.95
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.1871 (16), 11.352 (2), 11.378 (2)
α, β, γ (°)	84.53 (3), 73.15 (3), 74.02 (3)
V (Å³)	972.8 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	18.20
Crystal size (mm)	0.21 × 0.15 × 0.13

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.047, 0.094
No. of measured, independent and observed [I > 2σ(I)] reflections	8635, 3507, 3072
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.047, 0.98
No. of reflections	3507
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −1.19

Computer programs: CrystalClear (Rigaku, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Natural Science Foundation of Jiangsu High School (10KJB430005) and the Foundation of Jiangsu University (08JDG036).

References

Ni, W. X., Li, M., Zhan, S. Z., Hou, J. Z. & Li, D. (2009). Inorg. Chem. 48, 1433–1441. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, F., Huang, W. & You, X. Z. (2010). Dalton Trans. 39, 10652–10658. Web of Science CSD CrossRef CAS PubMed Google Scholar

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