Octa-kis(dimethyl sulfoxide-κO)cerium(III) μ(6)-oxido-dodeca-μ(2)-oxido-hexa-oxidohexa-molybdate(VI) dimethyl sulfoxide tetrasolvate.

The title complex, [Ce(C(2)H(6)OS)(8)](2)[Mo(6)O(19)](3)·4C(2)H(6)OS, was obtained as a byproduct of the reaction of [(C(4)H(9))(4)N](2)[Mo(6)O(19)] with Ce(NO(3))(3)·6H(2)O and phthalic acid in dimethyl-sulfoxide solution. The asymmetric unit consists of a complex [Ce(C(2)H(6)OS)(8)](3+) cation, one and a half of the Lindqvist-type [Mo(6)O(19)](2-) polyanions and two dimethyl-sulfoxide solvent mol-ecules; the half polyanion lies on an inversion center. The Ce(3+) ion is coordinated by eight dimethyl-sulfoxide ligands through the O atoms in the form of a distorted square antiprism. The Ce-O bond lengths range from 2.429 (6) to 2.550 (5) Å. The cohesion of the structure is ensured by S⋯O [3.115 (6), 3.242 (10) and 3.12 (3) Å], O⋯O [3.037 (10) Å] and C-H⋯O inter-actions between cations and anions. The S and C atoms of a dmso ligand are disordered over three sites in a 0.45:0.30:0.25 ratio. The dimethyl-sulfoxide solvent mol-ecules are highly disordered and could not be modelled successfully; their contribution was therefore removed from the refinement using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155]. Potential solvent-accessible voids of 500.0 Å(3) occur in the crystal structure.

Related literature

For general background, physical properties and applications of polyoxidometalates, see: Dolbecq et al. (2010 ▶). For the synthesis of [(C4H9)4N]2[Mo6O19], see: Hur et al. (1990 ▶). For related structures, see: Wang et al. (2003 ▶); Koo & Lee (2006 ▶); Qiu et al. (2006 ▶). For crystallographic analysis, see: Spek (2009 ▶).

Experimental

Crystal data

[Ce(C2H6OS)8]2[Mo6O19]3·4C2H6OS

M = 4481.72

Triclinic,

a = 13.4590 (2) Å

b = 15.4688 (3) Å

c = 17.6599 (4) Å

α = 90.281 (1)°

β = 98.468 (1)°

γ = 115.580 (1)°

V = 3270.48 (11) Å3

Z = 1

Mo Kα radiation

μ = 2.75 mm−1

T = 223 K

0.20 × 0.16 × 0.08 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.691, T max = 0.739

69065 measured reflections

12827 independent reflections

10059 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.159

S = 1.04

12827 reflections

680 parameters

H-atom parameters constrained

Δρmax = 2.47 e Å−3

Δρmin = −1.81 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: HKL-DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: HKL-DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812025949/pv2546sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025949/pv2546Isup2.hkl

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

[Ce(C2H6OS)8]2[Mo6O19]3·4C2H6OS	Z = 1
Mr = 4481.72	F(000) = 2168
Triclinic, P1	Dx = 2.117 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 13.4590 (2) Å	Cell parameters from 80805 reflections
b = 15.4688 (3) Å	θ = 2.3–29.9°
c = 17.6599 (4) Å	µ = 2.75 mm−1
α = 90.281 (1)°	T = 223 K
β = 98.468 (1)°	Prism, yellow
γ = 115.580 (1)°	0.20 × 0.16 × 0.08 mm
V = 3270.48 (11) Å3

Bruker–Nonius KappaCCD diffractometer	12827 independent reflections
Radiation source: fine-focus sealed tube	10059 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
φ & ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −16→16
Tmin = 0.691, Tmax = 0.739	k = −19→19
69065 measured reflections	l = −21→21

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.082P)2 + 11.5151P] where P = (Fo2 + 2Fc2)/3
12827 reflections	(Δ/σ)max < 0.001
680 parameters	Δρmax = 2.47 e Å−3
0 restraints	Δρmin = −1.81 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Ce1	0.37882 (3)	0.20892 (3)	0.24041 (2)	0.03716 (12)
Mo1	0.67824 (6)	0.92294 (5)	0.16090 (4)	0.04819 (18)
Mo2	0.54384 (6)	0.69998 (5)	0.19987 (4)	0.05286 (19)
Mo8	−0.00354 (7)	0.45025 (6)	0.12342 (4)	0.0570 (2)
Mo4	0.77556 (7)	0.98658 (5)	0.34389 (4)	0.0617 (2)
Mo7	0.18589 (6)	0.60787 (6)	0.03598 (5)	0.0629 (2)
Mo6	0.64036 (7)	0.76231 (5)	0.38286 (4)	0.0564 (2)
Mo3	0.81409 (6)	0.81761 (6)	0.25863 (5)	0.0596 (2)
Mo5	0.50644 (7)	0.87007 (7)	0.28498 (5)	0.0656 (2)
Mo9	−0.05413 (8)	0.61545 (6)	0.03477 (5)	0.0679 (2)
S1	0.24857 (17)	0.08769 (17)	0.40375 (12)	0.0534 (5)
S2A	0.2195 (8)	−0.0474 (7)	0.1700 (6)	0.062 (2)	0.45
C3A	0.3010 (13)	−0.0760 (10)	0.1039 (10)	0.107 (4)	0.45
H3A1	0.2621	−0.0869	0.0521	0.160*	0.45
H3A2	0.3088	−0.1327	0.1188	0.160*	0.45
H3A3	0.3736	−0.0230	0.1072	0.160*	0.45
C4A	0.0865 (19)	−0.097 (2)	0.107 (3)	0.142 (19)	0.45
H4A1	0.0373	−0.0755	0.1263	0.213*	0.45
H4A2	0.0545	−0.1662	0.1055	0.213*	0.45
H4A3	0.0967	−0.0769	0.0566	0.213*	0.45
S2B	0.2032 (7)	−0.0376 (6)	0.1133 (5)	0.0618 (19)	0.30
C3B	0.3010 (13)	−0.0760 (10)	0.1039 (10)	0.107 (4)	0.30
H3B1	0.3444	−0.0410	0.0663	0.160*	0.30
H3B2	0.2651	−0.1434	0.0878	0.160*	0.30
H3B3	0.3491	−0.0656	0.1523	0.160*	0.30
C4B	0.151 (3)	−0.121 (2)	0.186 (2)	0.133 (12)	0.30
H4B1	0.0904	−0.1135	0.2026	0.200*	0.30
H4B2	0.2101	−0.1072	0.2284	0.200*	0.30
H4B3	0.1256	−0.1853	0.1642	0.200*	0.30
S2C	0.2722 (17)	−0.0281 (16)	0.1755 (13)	0.083 (6)	0.25
C3C	0.3010 (13)	−0.0760 (10)	0.1039 (10)	0.107 (4)	0.25
H3C1	0.3707	−0.0312	0.0906	0.160*	0.25
H3C2	0.2428	−0.0913	0.0604	0.160*	0.25
H3C3	0.3065	−0.1336	0.1188	0.160*	0.25
C4C	0.151 (3)	−0.121 (2)	0.186 (2)	0.133 (12)	0.25
H4C1	0.1204	−0.1034	0.2256	0.200*	0.25
H4C2	0.1642	−0.1754	0.1989	0.200*	0.25
H4C3	0.0997	−0.1361	0.1383	0.200*	0.25
S3	0.07310 (18)	0.13552 (17)	0.20031 (15)	0.0617 (6)
S4	0.30340 (18)	0.37390 (15)	0.34142 (14)	0.0560 (5)
S5	0.30121 (18)	0.31060 (16)	0.06817 (12)	0.0511 (5)
S6	0.60406 (19)	0.45084 (16)	0.24827 (15)	0.0590 (5)
S7	0.5942 (2)	0.22013 (18)	0.13221 (16)	0.0656 (6)
S8	0.5973 (2)	0.2100 (2)	0.39721 (14)	0.0680 (6)
O1	0.5842 (5)	0.7923 (4)	0.1237 (3)	0.0553 (14)
O2	0.7666 (6)	1.0238 (4)	0.2402 (4)	0.0665 (17)
O3	0.8010 (5)	0.8888 (4)	0.1729 (3)	0.0564 (14)
O4	0.5505 (6)	0.9284 (5)	0.1907 (4)	0.0659 (17)
O5	0.6949 (6)	0.9812 (5)	0.0800 (4)	0.0744 (19)
O6	0.5536 (5)	0.6627 (4)	0.3044 (4)	0.0633 (16)
O7	0.6927 (6)	0.7071 (5)	0.2042 (4)	0.0648 (16)
O8	0.4430 (5)	0.7471 (5)	0.2238 (4)	0.0658 (17)
O9	0.4633 (7)	0.5952 (5)	0.1479 (4)	0.084 (2)
O10	0.7699 (5)	0.7586 (5)	0.3529 (4)	0.0665 (17)
O11	0.8772 (5)	0.9393 (5)	0.3200 (4)	0.0699 (18)
O12	0.9270 (7)	0.8005 (8)	0.2518 (6)	0.105 (3)
O13	0.7362 (6)	0.8943 (4)	0.4187 (3)	0.0646 (17)
O14	0.6301 (7)	0.9819 (5)	0.3400 (4)	0.079 (2)
O15	0.8613 (8)	1.0899 (5)	0.3958 (5)	0.102 (3)
O16	0.5197 (6)	0.7980 (5)	0.3720 (4)	0.0687 (18)
O17	0.3937 (8)	0.8861 (8)	0.2945 (6)	0.115 (3)
O18	0.6276 (8)	0.7041 (6)	0.4632 (4)	0.093 (3)
O19	0.6601 (4)	0.8432 (3)	0.2719 (3)	0.0357 (10)
O20	0.3191 (6)	0.6918 (6)	0.0598 (5)	0.097 (3)
O21	0.1477 (5)	0.5494 (4)	0.1283 (3)	0.0607 (15)
O22	0.1947 (6)	0.4962 (7)	0.0006 (4)	0.082 (2)
O23	0.1046 (6)	0.6812 (4)	0.0549 (4)	0.0746 (19)
O24	−0.0059 (7)	0.4147 (6)	0.2128 (4)	0.086 (2)
O25	0.0428 (6)	0.3671 (4)	0.0728 (4)	0.0675 (17)
O26	−0.0469 (6)	0.5526 (6)	0.1282 (3)	0.0725 (19)
O27	−0.1511 (5)	0.3721 (5)	0.0729 (4)	0.074 (2)
O28	−0.0966 (9)	0.6975 (7)	0.0588 (6)	0.112 (3)
O29	0.0000	0.5000	0.0000	0.0404 (15)
O32	0.2459 (5)	0.1094 (6)	0.3214 (4)	0.083 (2)
O33	0.2578 (7)	0.0589 (5)	0.1608 (5)	0.088 (2)
O34	0.1906 (5)	0.2087 (5)	0.1954 (4)	0.0674 (18)
O35	0.3861 (6)	0.3394 (5)	0.3216 (4)	0.0667 (17)
O36	0.3887 (5)	0.3088 (4)	0.1325 (3)	0.0561 (14)
O37	0.5755 (4)	0.3460 (4)	0.2596 (4)	0.0529 (13)
O38	0.4921 (5)	0.1623 (5)	0.1676 (5)	0.0730 (19)
O39	0.4834 (5)	0.1710 (5)	0.3498 (4)	0.0627 (16)
C1	0.215 (2)	−0.0349 (12)	0.4032 (12)	0.157 (9)
H1A	0.1498	−0.0702	0.3657	0.235*
H1B	0.2007	−0.0566	0.4531	0.235*
H1C	0.2764	−0.0451	0.3907	0.235*
C2	0.1235 (10)	0.0805 (15)	0.4247 (7)	0.118 (6)
H2A	0.1006	0.1209	0.3928	0.178*
H2B	0.1333	0.1014	0.4777	0.178*
H2C	0.0673	0.0152	0.4153	0.178*
C5	0.0023 (11)	0.1194 (16)	0.1039 (8)	0.147 (8)
H5A	0.0192	0.1811	0.0841	0.221*
H5B	−0.0768	0.0851	0.1028	0.221*
H5C	0.0263	0.0834	0.0727	0.221*
C6	0.0146 (11)	0.2028 (11)	0.2400 (12)	0.122 (6)
H6A	0.0433	0.2170	0.2940	0.184*
H6B	−0.0651	0.1667	0.2325	0.184*
H6C	0.0336	0.2618	0.2154	0.184*
C7	0.3831 (9)	0.4713 (7)	0.4113 (6)	0.071 (3)
H7A	0.4101	0.4482	0.4563	0.107*
H7B	0.3371	0.5004	0.4245	0.107*
H7C	0.4453	0.5180	0.3909	0.107*
C8	0.2828 (10)	0.4397 (8)	0.2643 (7)	0.083 (3)
H8A	0.3534	0.4903	0.2575	0.124*
H8B	0.2340	0.4669	0.2752	0.124*
H8C	0.2499	0.3977	0.2182	0.124*
C9	0.3816 (10)	0.3976 (8)	0.0101 (6)	0.079 (3)
H9A	0.4085	0.4606	0.0354	0.119*
H9B	0.3361	0.3936	−0.0383	0.119*
H9C	0.4438	0.3861	0.0017	0.119*
C10	0.2637 (11)	0.2072 (9)	0.0099 (6)	0.079 (3)
H10A	0.3298	0.2024	0.0007	0.118*
H10B	0.2216	0.2098	−0.0382	0.118*
H10C	0.2191	0.1520	0.0348	0.118*
C11	0.7005 (16)	0.5176 (9)	0.3288 (10)	0.134 (7)
H11A	0.7070	0.5819	0.3307	0.201*
H11B	0.7720	0.5195	0.3255	0.201*
H11C	0.6755	0.4881	0.3745	0.201*
C12	0.6920 (16)	0.4827 (9)	0.1786 (10)	0.120 (6)
H12A	0.7466	0.4582	0.1902	0.180*
H12B	0.7292	0.5514	0.1787	0.180*
H12C	0.6484	0.4558	0.1289	0.180*
C13	0.7069 (10)	0.2150 (10)	0.1954 (9)	0.094 (4)
H13A	0.6795	0.1574	0.2220	0.141*
H13B	0.7401	0.2700	0.2320	0.141*
H13C	0.7618	0.2149	0.1664	0.141*
C14	0.5824 (14)	0.1392 (10)	0.0555 (8)	0.103 (4)
H14A	0.6158	0.0981	0.0742	0.155*
H14B	0.6201	0.1751	0.0158	0.155*
H14C	0.5050	0.1008	0.0351	0.155*
C15	0.6047 (13)	0.3028 (10)	0.4582 (8)	0.098 (4)
H15A	0.5785	0.3432	0.4289	0.147*
H15B	0.6806	0.3402	0.4824	0.147*
H15C	0.5589	0.2759	0.4967	0.147*
C16	0.5840 (13)	0.1237 (10)	0.4661 (7)	0.096 (4)
H16A	0.5092	0.0958	0.4772	0.143*
H16B	0.6357	0.1546	0.5124	0.143*
H16C	0.6000	0.0742	0.4460	0.143*

	U11	U22	U33	U12	U13	U23
Ce1	0.0368 (2)	0.0356 (2)	0.0368 (2)	0.01406 (17)	0.00461 (15)	0.00387 (15)
Mo1	0.0585 (4)	0.0430 (4)	0.0388 (4)	0.0190 (3)	0.0054 (3)	0.0099 (3)
Mo2	0.0586 (4)	0.0373 (4)	0.0421 (4)	0.0049 (3)	−0.0013 (3)	−0.0038 (3)
Mo8	0.0630 (4)	0.0590 (4)	0.0385 (4)	0.0203 (4)	−0.0025 (3)	0.0123 (3)
Mo4	0.0741 (5)	0.0387 (4)	0.0449 (4)	0.0031 (3)	−0.0025 (3)	−0.0052 (3)
Mo7	0.0478 (4)	0.0588 (5)	0.0571 (5)	0.0057 (4)	−0.0093 (3)	0.0092 (4)
Mo6	0.0700 (5)	0.0473 (4)	0.0356 (4)	0.0119 (4)	0.0042 (3)	0.0096 (3)
Mo3	0.0480 (4)	0.0693 (5)	0.0680 (5)	0.0320 (4)	0.0080 (3)	0.0134 (4)
Mo5	0.0579 (5)	0.0801 (6)	0.0713 (5)	0.0390 (4)	0.0193 (4)	0.0070 (4)
Mo9	0.0907 (6)	0.0627 (5)	0.0598 (5)	0.0488 (5)	−0.0080 (4)	−0.0070 (4)
S1	0.0471 (10)	0.0615 (13)	0.0419 (10)	0.0161 (10)	0.0029 (8)	0.0059 (9)
S2A	0.074 (5)	0.044 (5)	0.054 (4)	0.011 (4)	0.015 (5)	−0.002 (3)
C3A	0.117 (11)	0.066 (7)	0.131 (12)	0.034 (7)	0.020 (9)	−0.008 (7)
C4A	0.039 (12)	0.076 (19)	0.27 (5)	0.005 (12)	−0.03 (2)	−0.08 (3)
S2B	0.077 (5)	0.059 (4)	0.040 (4)	0.024 (4)	−0.001 (4)	−0.008 (3)
C3B	0.117 (11)	0.066 (7)	0.131 (12)	0.034 (7)	0.020 (9)	−0.008 (7)
C4B	0.16 (3)	0.073 (17)	0.15 (3)	0.019 (19)	0.08 (3)	0.014 (17)
S2C	0.102 (13)	0.057 (10)	0.073 (9)	0.017 (11)	0.014 (12)	0.014 (7)
C3C	0.117 (11)	0.066 (7)	0.131 (12)	0.034 (7)	0.020 (9)	−0.008 (7)
C4C	0.16 (3)	0.073 (17)	0.15 (3)	0.019 (19)	0.08 (3)	0.014 (17)
S3	0.0461 (11)	0.0552 (12)	0.0770 (15)	0.0163 (10)	0.0080 (10)	0.0262 (11)
S4	0.0509 (11)	0.0455 (11)	0.0668 (14)	0.0143 (9)	0.0176 (10)	−0.0035 (9)
S5	0.0577 (11)	0.0559 (12)	0.0407 (10)	0.0245 (10)	0.0123 (9)	0.0128 (9)
S6	0.0571 (12)	0.0432 (11)	0.0741 (15)	0.0198 (10)	0.0099 (11)	0.0076 (10)
S7	0.0771 (15)	0.0561 (13)	0.0763 (16)	0.0358 (12)	0.0292 (13)	0.0122 (11)
S8	0.0561 (13)	0.1000 (19)	0.0481 (12)	0.0357 (13)	0.0042 (10)	0.0070 (12)
O1	0.062 (3)	0.055 (3)	0.032 (3)	0.013 (3)	−0.003 (2)	−0.001 (2)
O2	0.082 (4)	0.042 (3)	0.060 (4)	0.015 (3)	0.003 (3)	0.005 (3)
O3	0.052 (3)	0.063 (4)	0.050 (3)	0.019 (3)	0.017 (3)	0.008 (3)
O4	0.071 (4)	0.070 (4)	0.066 (4)	0.045 (4)	−0.006 (3)	0.004 (3)
O5	0.097 (5)	0.068 (4)	0.050 (4)	0.029 (4)	0.012 (3)	0.025 (3)
O6	0.075 (4)	0.042 (3)	0.050 (3)	0.006 (3)	0.004 (3)	0.006 (3)
O7	0.082 (4)	0.062 (4)	0.062 (4)	0.043 (4)	0.011 (3)	−0.003 (3)
O8	0.040 (3)	0.077 (4)	0.062 (4)	0.010 (3)	0.003 (3)	0.002 (3)
O9	0.105 (6)	0.043 (3)	0.061 (4)	−0.003 (4)	0.002 (4)	−0.011 (3)
O10	0.064 (4)	0.063 (4)	0.066 (4)	0.026 (3)	−0.007 (3)	0.014 (3)
O11	0.043 (3)	0.066 (4)	0.069 (4)	0.001 (3)	−0.010 (3)	0.008 (3)
O12	0.080 (5)	0.148 (9)	0.122 (7)	0.080 (6)	0.023 (5)	0.031 (6)
O13	0.080 (4)	0.054 (3)	0.032 (3)	0.007 (3)	−0.003 (3)	−0.002 (2)
O14	0.112 (6)	0.063 (4)	0.075 (5)	0.045 (4)	0.036 (4)	−0.003 (3)
O15	0.122 (7)	0.051 (4)	0.075 (5)	−0.010 (4)	−0.005 (5)	−0.023 (4)
O16	0.069 (4)	0.079 (4)	0.046 (3)	0.016 (3)	0.024 (3)	0.004 (3)
O17	0.089 (6)	0.157 (9)	0.139 (9)	0.082 (7)	0.046 (6)	0.020 (7)
O18	0.125 (7)	0.075 (5)	0.046 (4)	0.016 (5)	0.005 (4)	0.021 (3)
O19	0.036 (2)	0.029 (2)	0.032 (2)	0.0066 (19)	−0.0001 (19)	−0.0017 (18)
O20	0.060 (4)	0.094 (6)	0.088 (6)	−0.005 (4)	−0.014 (4)	0.017 (5)
O21	0.060 (3)	0.058 (4)	0.045 (3)	0.017 (3)	−0.017 (3)	0.004 (3)
O22	0.054 (4)	0.129 (7)	0.066 (4)	0.044 (4)	0.003 (3)	0.019 (4)
O23	0.098 (5)	0.034 (3)	0.070 (4)	0.016 (3)	−0.010 (4)	−0.002 (3)
O24	0.099 (5)	0.103 (6)	0.047 (4)	0.038 (5)	0.005 (4)	0.029 (4)
O25	0.095 (5)	0.050 (3)	0.055 (4)	0.037 (3)	−0.009 (3)	0.010 (3)
O26	0.096 (5)	0.098 (5)	0.037 (3)	0.056 (4)	0.006 (3)	−0.001 (3)
O27	0.057 (4)	0.070 (4)	0.067 (4)	0.004 (3)	0.003 (3)	0.027 (3)
O28	0.158 (9)	0.113 (7)	0.098 (6)	0.103 (7)	−0.013 (6)	−0.018 (5)
O29	0.043 (4)	0.036 (4)	0.034 (4)	0.013 (3)	−0.006 (3)	−0.002 (3)
O32	0.055 (4)	0.103 (6)	0.054 (4)	0.002 (4)	0.006 (3)	0.035 (4)
O33	0.085 (5)	0.037 (3)	0.118 (7)	0.003 (3)	0.016 (4)	−0.032 (4)
O34	0.040 (3)	0.068 (4)	0.095 (5)	0.023 (3)	0.013 (3)	0.036 (4)
O35	0.075 (4)	0.066 (4)	0.065 (4)	0.037 (3)	0.008 (3)	−0.008 (3)
O36	0.057 (3)	0.059 (3)	0.042 (3)	0.016 (3)	0.005 (2)	0.016 (3)
O37	0.044 (3)	0.037 (3)	0.066 (4)	0.007 (2)	0.009 (3)	0.007 (2)
O38	0.060 (4)	0.062 (4)	0.101 (5)	0.025 (3)	0.032 (4)	−0.005 (4)
O39	0.053 (3)	0.069 (4)	0.063 (4)	0.028 (3)	−0.005 (3)	0.015 (3)
C1	0.28 (3)	0.083 (10)	0.135 (15)	0.095 (15)	0.066 (16)	0.039 (10)
C2	0.074 (7)	0.24 (2)	0.052 (6)	0.083 (10)	0.008 (5)	0.006 (9)
C5	0.073 (8)	0.22 (2)	0.068 (8)	−0.002 (10)	−0.014 (6)	0.035 (10)
C6	0.064 (7)	0.109 (11)	0.203 (18)	0.030 (7)	0.071 (10)	0.033 (11)
C7	0.080 (7)	0.055 (5)	0.072 (6)	0.023 (5)	0.009 (5)	−0.012 (5)
C8	0.083 (7)	0.068 (7)	0.092 (8)	0.030 (6)	0.007 (6)	0.003 (6)
C9	0.091 (7)	0.069 (6)	0.062 (6)	0.019 (6)	0.019 (5)	0.031 (5)
C10	0.104 (8)	0.085 (7)	0.051 (5)	0.046 (7)	0.009 (5)	0.006 (5)
C11	0.170 (15)	0.057 (7)	0.117 (12)	0.021 (9)	−0.057 (11)	−0.010 (7)
C12	0.184 (16)	0.063 (7)	0.127 (12)	0.045 (9)	0.095 (12)	0.034 (8)
C13	0.064 (6)	0.090 (9)	0.128 (11)	0.034 (6)	0.014 (7)	0.032 (8)
C14	0.139 (12)	0.091 (9)	0.090 (9)	0.053 (9)	0.046 (9)	0.001 (7)
C15	0.116 (10)	0.086 (8)	0.076 (8)	0.033 (8)	0.006 (7)	0.004 (6)
C16	0.141 (11)	0.103 (9)	0.065 (7)	0.082 (9)	−0.009 (7)	0.008 (6)

Ce1—O35	2.429 (6)	C4A—H4A3	0.9600
Ce1—O36	2.441 (5)	S2B—O33	1.526 (10)
Ce1—O39	2.445 (6)	S2B—C4B	1.81 (3)
Ce1—O32	2.453 (6)	C4B—H4B1	0.9600
Ce1—O38	2.453 (6)	C4B—H4B2	0.9600
Ce1—O33	2.459 (6)	C4B—H4B3	0.9600
Ce1—O34	2.539 (6)	S2C—O33	1.46 (3)
Ce1—O37	2.550 (5)	S3—O34	1.512 (6)
Mo1—O5	1.684 (6)	S3—C6	1.749 (15)
Mo1—O4	1.906 (7)	S3—C5	1.785 (13)
Mo1—O1	1.911 (6)	S4—O35	1.507 (7)
Mo1—O2	1.923 (6)	S4—C8	1.765 (12)
Mo1—O3	1.925 (6)	S4—C7	1.771 (10)
Mo1—O19	2.309 (4)	S5—O36	1.521 (6)
Mo2—O9	1.680 (6)	S5—C10	1.735 (12)
Mo2—O8	1.890 (7)	S5—C9	1.765 (9)
Mo2—O1	1.926 (6)	S6—O37	1.518 (6)
Mo2—O6	1.940 (6)	S6—C11	1.749 (13)
Mo2—O7	1.949 (7)	S6—C12	1.757 (13)
Mo2—O19	2.317 (4)	S7—O38	1.508 (7)
Mo8—O24	1.675 (6)	S7—C13	1.776 (12)
Mo8—O27	1.896 (6)	S7—C14	1.782 (13)
Mo8—O26	1.915 (7)	S8—O39	1.495 (6)
Mo8—O25	1.922 (7)	S8—C15	1.749 (14)
Mo8—O21	1.938 (6)	S8—C16	1.780 (12)
Mo8—O29	2.3153 (7)	O22—Mo9i	1.942 (8)
Mo4—O15	1.676 (7)	O25—Mo9i	1.938 (7)
Mo4—O11	1.901 (8)	O27—Mo7i	1.969 (7)
Mo4—O13	1.907 (6)	O29—Mo9i	2.3113 (8)
Mo4—O14	1.918 (8)	O29—Mo8i	2.3153 (7)
Mo4—O2	1.925 (6)	O29—Mo7i	2.3160 (7)
Mo4—O19	2.316 (4)	C1—H1A	0.9600
Mo7—O20	1.685 (7)	C1—H1B	0.9600
Mo7—O22	1.892 (9)	C1—H1C	0.9600
Mo7—O21	1.897 (6)	C2—H2A	0.9600
Mo7—O23	1.943 (8)	C2—H2B	0.9600
Mo7—O27i	1.969 (7)	C2—H2C	0.9600
Mo7—O29	2.3160 (7)	C5—H5A	0.9600
Mo6—O18	1.674 (7)	C5—H5B	0.9600
Mo6—O6	1.899 (6)	C5—H5C	0.9600
Mo6—O16	1.915 (7)	C6—H6A	0.9600
Mo6—O10	1.919 (7)	C6—H6B	0.9600
Mo6—O13	1.925 (6)	C6—H6C	0.9600
Mo6—O19	2.316 (4)	C7—H7A	0.9600
Mo3—O12	1.672 (7)	C7—H7B	0.9600
Mo3—O7	1.904 (7)	C7—H7C	0.9600
Mo3—O3	1.908 (6)	C8—H8A	0.9600
Mo3—O11	1.941 (7)	C8—H8B	0.9600
Mo3—O10	1.948 (7)	C8—H8C	0.9600
Mo3—O19	2.314 (5)	C9—H9A	0.9600
Mo5—O17	1.671 (7)	C9—H9B	0.9600
Mo5—O14	1.931 (8)	C9—H9C	0.9600
Mo5—O16	1.935 (7)	C10—H10A	0.9600
Mo5—O4	1.944 (7)	C10—H10B	0.9600
Mo5—O8	1.954 (7)	C10—H10C	0.9600
Mo5—O19	2.321 (5)	C11—H11A	0.9600
Mo9—O28	1.676 (8)	C11—H11B	0.9600
Mo9—O23	1.903 (8)	C11—H11C	0.9600
Mo9—O26	1.930 (7)	C12—H12A	0.9600
Mo9—O25i	1.938 (7)	C12—H12B	0.9600
Mo9—O22i	1.942 (8)	C12—H12C	0.9600
Mo9—O29	2.3113 (8)	C13—H13A	0.9600
S1—O32	1.492 (7)	C13—H13B	0.9600
S1—C2	1.734 (11)	C13—H13C	0.9600
S1—C1	1.749 (15)	C14—H14A	0.9600
S2A—O33	1.514 (13)	C14—H14B	0.9600
S2A—C4A	1.80 (3)	C14—H14C	0.9600
S2A—C3A	1.884 (18)	C15—H15A	0.9600
C3A—H3A1	0.9600	C15—H15B	0.9600
C3A—H3A2	0.9600	C15—H15C	0.9600
C3A—H3A3	0.9600	C16—H16A	0.9600
C4A—H4A1	0.9600	C16—H16B	0.9600
C4A—H4A2	0.9600	C16—H16C	0.9600
O8···O20	3.037 (11)	O13···S1ii	3.115 (6)
O28···S5i	3.242 (12)	O17···S2Ciii	3.12 (3)
O35—Ce1—O36	87.8 (2)	O33—S2B—C4B	101.6 (12)
O35—Ce1—O39	88.2 (2)	S2B—C4B—H4B1	109.5
O36—Ce1—O39	146.3 (2)	S2B—C4B—H4B2	109.5
O35—Ce1—O32	82.8 (3)	H4B1—C4B—H4B2	109.5
O36—Ce1—O32	140.4 (2)	S2B—C4B—H4B3	109.5
O39—Ce1—O32	71.9 (2)	H4B1—C4B—H4B3	109.5
O35—Ce1—O38	142.6 (2)	H4B2—C4B—H4B3	109.5
O36—Ce1—O38	80.2 (2)	O34—S3—C6	103.8 (5)
O39—Ce1—O38	82.9 (3)	O34—S3—C5	103.1 (6)
O32—Ce1—O38	127.6 (3)	C6—S3—C5	98.3 (10)
O35—Ce1—O33	146.0 (3)	O35—S4—C8	105.7 (5)
O36—Ce1—O33	93.3 (3)	O35—S4—C7	104.3 (5)
O39—Ce1—O33	108.2 (3)	C8—S4—C7	98.6 (6)
O32—Ce1—O33	74.9 (3)	O36—S5—C10	104.0 (5)
O38—Ce1—O33	70.6 (3)	O36—S5—C9	103.2 (5)
O35—Ce1—O34	77.2 (2)	C10—S5—C9	99.7 (6)
O36—Ce1—O34	69.5 (2)	O37—S6—C11	106.5 (5)
O39—Ce1—O34	141.4 (2)	O37—S6—C12	105.3 (5)
O32—Ce1—O34	71.0 (2)	C11—S6—C12	99.7 (10)
O38—Ce1—O34	129.1 (3)	O38—S7—C13	104.8 (5)
O33—Ce1—O34	71.5 (3)	O38—S7—C14	102.3 (6)
O35—Ce1—O37	70.7 (2)	C13—S7—C14	99.2 (8)
O36—Ce1—O37	72.73 (19)	O39—S8—C15	105.0 (6)
O39—Ce1—O37	74.4 (2)	O39—S8—C16	103.4 (6)
O32—Ce1—O37	137.3 (2)	C15—S8—C16	98.2 (6)
O38—Ce1—O37	71.9 (2)	Mo1—O1—Mo2	116.5 (3)
O33—Ce1—O37	141.7 (2)	Mo1—O2—Mo4	116.8 (3)
O34—Ce1—O37	130.61 (19)	Mo3—O3—Mo1	116.7 (3)
O5—Mo1—O4	104.1 (3)	Mo1—O4—Mo5	116.3 (3)
O5—Mo1—O1	103.2 (3)	Mo6—O6—Mo2	117.0 (3)
O4—Mo1—O1	87.7 (3)	Mo3—O7—Mo2	116.9 (3)
O5—Mo1—O2	103.1 (3)	Mo2—O8—Mo5	117.2 (3)
O4—Mo1—O2	86.9 (3)	Mo6—O10—Mo3	116.5 (3)
O1—Mo1—O2	153.7 (2)	Mo4—O11—Mo3	117.0 (3)
O5—Mo1—O3	101.8 (3)	Mo4—O13—Mo6	117.8 (3)
O4—Mo1—O3	154.1 (3)	Mo4—O14—Mo5	116.2 (3)
O1—Mo1—O3	87.0 (3)	Mo6—O16—Mo5	116.5 (3)
O2—Mo1—O3	86.6 (3)	Mo1—O19—Mo3	89.79 (16)
O5—Mo1—O19	178.5 (3)	Mo1—O19—Mo4	90.22 (15)
O4—Mo1—O19	77.4 (2)	Mo3—O19—Mo4	90.06 (15)
O1—Mo1—O19	77.11 (19)	Mo1—O19—Mo6	179.5 (2)
O2—Mo1—O19	76.6 (2)	Mo3—O19—Mo6	90.51 (16)
O3—Mo1—O19	76.7 (2)	Mo4—O19—Mo6	90.18 (15)
O9—Mo2—O8	104.9 (4)	Mo1—O19—Mo2	89.70 (15)
O9—Mo2—O1	103.7 (3)	Mo3—O19—Mo2	90.26 (16)
O8—Mo2—O1	88.4 (3)	Mo4—O19—Mo2	179.7 (2)
O9—Mo2—O6	103.4 (3)	Mo6—O19—Mo2	89.89 (15)
O8—Mo2—O6	87.5 (3)	Mo1—O19—Mo5	89.87 (16)
O1—Mo2—O6	152.7 (2)	Mo3—O19—Mo5	179.5 (2)
O9—Mo2—O7	102.1 (4)	Mo4—O19—Mo5	89.64 (16)
O8—Mo2—O7	153.0 (3)	Mo6—O19—Mo5	89.83 (16)
O1—Mo2—O7	85.8 (3)	Mo2—O19—Mo5	90.04 (15)
O6—Mo2—O7	85.7 (3)	Mo7—O21—Mo8	116.7 (3)
O9—Mo2—O19	178.0 (3)	Mo7—O22—Mo9i	116.7 (3)
O8—Mo2—O19	77.0 (2)	Mo9—O23—Mo7	117.0 (3)
O1—Mo2—O19	76.6 (2)	Mo8—O25—Mo9i	116.2 (3)
O6—Mo2—O19	76.2 (2)	Mo8—O26—Mo9	116.4 (3)
O7—Mo2—O19	76.0 (2)	Mo8—O27—Mo7i	116.4 (3)
O24—Mo8—O27	102.8 (3)	Mo9—O29—Mo9i	180.00 (4)
O24—Mo8—O26	102.9 (4)	Mo9—O29—Mo8i	90.16 (3)
O27—Mo8—O26	87.2 (3)	Mo9i—O29—Mo8i	89.84 (3)
O24—Mo8—O25	103.2 (4)	Mo9—O29—Mo8	89.84 (3)
O27—Mo8—O25	87.7 (3)	Mo9i—O29—Mo8	90.16 (3)
O26—Mo8—O25	153.9 (3)	Mo8i—O29—Mo8	180.00 (4)
O24—Mo8—O21	103.4 (3)	Mo9—O29—Mo7	90.27 (4)
O27—Mo8—O21	153.7 (3)	Mo9i—O29—Mo7	89.73 (4)
O26—Mo8—O21	86.5 (3)	Mo8i—O29—Mo7	90.36 (3)
O25—Mo8—O21	86.8 (3)	Mo8—O29—Mo7	89.64 (3)
O24—Mo8—O29	179.8 (4)	Mo9—O29—Mo7i	89.73 (4)
O27—Mo8—O29	77.30 (19)	Mo9i—O29—Mo7i	90.27 (4)
O26—Mo8—O29	76.98 (19)	Mo8i—O29—Mo7i	89.64 (3)
O25—Mo8—O29	76.94 (18)	Mo8—O29—Mo7i	90.36 (3)
O21—Mo8—O29	76.45 (17)	Mo7—O29—Mo7i	180.0
O15—Mo4—O11	102.0 (4)	S1—O32—Ce1	137.2 (4)
O15—Mo4—O13	103.8 (4)	S2C—O33—S2B	51.3 (9)
O11—Mo4—O13	87.8 (3)	S2C—O33—Ce1	119.9 (10)
O15—Mo4—O14	103.9 (4)	S2A—O33—Ce1	136.0 (7)
O11—Mo4—O14	154.1 (3)	S2B—O33—Ce1	168.8 (6)
O13—Mo4—O14	86.8 (3)	S3—O34—Ce1	131.5 (3)
O15—Mo4—O2	103.6 (4)	S4—O35—Ce1	136.2 (4)
O11—Mo4—O2	87.4 (3)	S5—O36—Ce1	133.1 (3)
O13—Mo4—O2	152.5 (3)	S6—O37—Ce1	125.4 (3)
O14—Mo4—O2	85.7 (3)	S7—O38—Ce1	132.4 (4)
O15—Mo4—O19	178.9 (4)	S8—O39—Ce1	140.7 (4)
O11—Mo4—O19	76.8 (2)	S1—C1—H1A	109.5
O13—Mo4—O19	76.2 (2)	S1—C1—H1B	109.5
O14—Mo4—O19	77.2 (2)	H1A—C1—H1B	109.5
O2—Mo4—O19	76.4 (2)	S1—C1—H1C	109.5
O20—Mo7—O22	105.6 (4)	H1A—C1—H1C	109.5
O20—Mo7—O21	105.0 (3)	H1B—C1—H1C	109.5
O22—Mo7—O21	88.7 (3)	S1—C2—H2A	109.5
O20—Mo7—O23	101.3 (4)	S1—C2—H2B	109.5
O22—Mo7—O23	153.0 (3)	H2A—C2—H2B	109.5
O21—Mo7—O23	87.1 (3)	S1—C2—H2C	109.5
O20—Mo7—O27i	101.8 (3)	H2A—C2—H2C	109.5
O22—Mo7—O27i	86.6 (3)	H2B—C2—H2C	109.5
O21—Mo7—O27i	153.1 (3)	S3—C5—H5A	109.5
O23—Mo7—O27i	85.2 (3)	S3—C5—H5B	109.5
O20—Mo7—O29	176.4 (3)	H5A—C5—H5B	109.5
O22—Mo7—O29	77.2 (2)	S3—C5—H5C	109.5
O21—Mo7—O29	77.18 (17)	H5A—C5—H5C	109.5
O23—Mo7—O29	75.9 (2)	H5B—C5—H5C	109.5
O27i—Mo7—O29	75.94 (18)	S3—C6—H6A	109.5
O18—Mo6—O6	103.3 (3)	S3—C6—H6B	109.5
O18—Mo6—O16	103.5 (4)	H6A—C6—H6B	109.5
O6—Mo6—O16	87.7 (3)	S3—C6—H6C	109.5
O18—Mo6—O10	102.7 (4)	H6A—C6—H6C	109.5
O6—Mo6—O10	87.2 (3)	H6B—C6—H6C	109.5
O16—Mo6—O10	153.8 (3)	S4—C7—H7A	109.5
O18—Mo6—O13	103.9 (3)	S4—C7—H7B	109.5
O6—Mo6—O13	152.8 (2)	H7A—C7—H7B	109.5
O16—Mo6—O13	86.5 (3)	S4—C7—H7C	109.5
O10—Mo6—O13	86.3 (3)	H7A—C7—H7C	109.5
O18—Mo6—O19	179.3 (4)	H7B—C7—H7C	109.5
O6—Mo6—O19	76.9 (2)	S4—C8—H8A	109.5
O16—Mo6—O19	77.1 (2)	S4—C8—H8B	109.5
O10—Mo6—O19	76.7 (2)	H8A—C8—H8B	109.5
O13—Mo6—O19	75.9 (2)	S4—C8—H8C	109.5
O12—Mo3—O7	104.5 (4)	H8A—C8—H8C	109.5
O12—Mo3—O3	104.3 (4)	H8B—C8—H8C	109.5
O7—Mo3—O3	88.2 (3)	S5—C9—H9A	109.5
O12—Mo3—O11	102.5 (4)	S5—C9—H9B	109.5
O7—Mo3—O11	153.0 (3)	H9A—C9—H9B	109.5
O3—Mo3—O11	86.2 (3)	S5—C9—H9C	109.5
O12—Mo3—O10	102.6 (4)	H9A—C9—H9C	109.5
O7—Mo3—O10	87.3 (3)	H9B—C9—H9C	109.5
O3—Mo3—O10	153.0 (3)	S5—C10—H10A	109.5
O11—Mo3—O10	85.8 (3)	S5—C10—H10B	109.5
O12—Mo3—O19	178.3 (4)	H10A—C10—H10B	109.5
O7—Mo3—O19	76.9 (2)	S5—C10—H10C	109.5
O3—Mo3—O19	76.8 (2)	H10A—C10—H10C	109.5
O11—Mo3—O19	76.2 (2)	H10B—C10—H10C	109.5
O10—Mo3—O19	76.2 (2)	S6—C11—H11A	109.5
O17—Mo5—O14	104.5 (5)	S6—C11—H11B	109.5
O17—Mo5—O16	102.5 (4)	H11A—C11—H11B	109.5
O14—Mo5—O16	88.1 (3)	S6—C11—H11C	109.5
O17—Mo5—O4	104.5 (4)	H11A—C11—H11C	109.5
O14—Mo5—O4	87.4 (3)	H11B—C11—H11C	109.5
O16—Mo5—O4	152.9 (3)	S6—C12—H12A	109.5
O17—Mo5—O8	102.9 (5)	S6—C12—H12B	109.5
O14—Mo5—O8	152.6 (3)	H12A—C12—H12B	109.5
O16—Mo5—O8	85.9 (3)	S6—C12—H12C	109.5
O4—Mo5—O8	85.9 (3)	H12A—C12—H12C	109.5
O17—Mo5—O19	178.4 (4)	H12B—C12—H12C	109.5
O14—Mo5—O19	76.9 (2)	S7—C13—H13A	109.5
O16—Mo5—O19	76.6 (2)	S7—C13—H13B	109.5
O4—Mo5—O19	76.4 (2)	H13A—C13—H13B	109.5
O8—Mo5—O19	75.8 (2)	S7—C13—H13C	109.5
O28—Mo9—O23	104.6 (5)	H13A—C13—H13C	109.5
O28—Mo9—O26	103.5 (4)	H13B—C13—H13C	109.5
O23—Mo9—O26	88.0 (3)	S7—C14—H14A	109.5
O28—Mo9—O25i	102.9 (4)	S7—C14—H14B	109.5
O23—Mo9—O25i	86.8 (3)	H14A—C14—H14B	109.5
O26—Mo9—O25i	153.5 (3)	S7—C14—H14C	109.5
O28—Mo9—O22i	102.3 (5)	H14A—C14—H14C	109.5
O23—Mo9—O22i	153.1 (3)	H14B—C14—H14C	109.5
O26—Mo9—O22i	86.6 (3)	S8—C15—H15A	109.5
O25i—Mo9—O22i	86.4 (3)	S8—C15—H15B	109.5
O28—Mo9—O29	178.6 (4)	H15A—C15—H15B	109.5
O23—Mo9—O29	76.7 (2)	S8—C15—H15C	109.5
O26—Mo9—O29	76.8 (2)	H15A—C15—H15C	109.5
O25i—Mo9—O29	76.73 (19)	H15B—C15—H15C	109.5
O22i—Mo9—O29	76.4 (2)	S8—C16—H16A	109.5
O32—S1—C2	104.2 (5)	S8—C16—H16B	109.5
O32—S1—C1	105.1 (7)	H16A—C16—H16B	109.5
C2—S1—C1	97.7 (11)	S8—C16—H16C	109.5
O33—S2A—C4A	101.0 (15)	H16A—C16—H16C	109.5
O33—S2A—C3A	100.7 (7)	H16B—C16—H16C	109.5
C4A—S2A—C3A	97.5 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O13ii	0.96	2.32	3.030 (14)	130
C6—H6B···O2iv	0.96	2.41	3.291 (18)	153
C11—H11A···O10	0.96	2.50	3.437 (15)	166
C14—H14A···O5v	0.96	2.46	3.386 (19)	163
C14—H14B···O20vi	0.96	2.36	3.255 (17)	154
C16—H16C···O14v	0.96	2.53	3.420 (17)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O13i	0.96	2.32	3.030 (14)	130
C6—H6B⋯O2ii	0.96	2.41	3.291 (18)	153
C11—H11A⋯O10	0.96	2.50	3.437 (15)	166
C14—H14A⋯O5iii	0.96	2.46	3.386 (19)	163
C14—H14B⋯O20iv	0.96	2.36	3.255 (17)	154
C16—H16C⋯O14iii	0.96	2.53	3.420 (17)	154

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