Hexa-kis-(dimethyl sulfoxide-κO)calcium μ(6)-oxido-dodeca-kis-μ(2)-oxido-hexa-oxido-hexa-tungstate(VI).

In the title compound, [Ca(C(2)H(6)OS)(6)][W(6)O(19)], 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 octa-hedral geometry. The [W(6)O(19)](2-) isopolyanion possesses the well-known Lindqvist structure in which each W(VI) atom is coordinated by four μ(2)-O, one terminal O and one μ(6)-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 = 1915.95

Triclinic,

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[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.047

S = 0.98

3507 reflections

229 parameters

H-atom parameters constrained

Δρmax = 1.05 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812018338/rz2743sup1.cif

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

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

[Ca(C2H6OS)6][W6O19]	Z = 1
Mr = 1915.95	F(000) = 868
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0163P)2] where P = (Fo2 + 2Fc2)/3
3507 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 1.05 e Å−3
0 restraints	Δρmin = −1.19 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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)