Poly[diaqua­hexa­kis­(dimeth­yl sulfoxide-κO)cerium [(μ₂-hexa­cosa­oxoocta­molybdate)sodium]]

The title compound, {[Ce(C₂H₆OS)₆(H₂O)₂][NaMo₈O₂₆]}_n, contains an infinite chain of β-octa­molybdate moieties linked by Na⁺ ions, and further linked into a two-dimensional network by [Ce(DMSO)₆(H₂O)₂]³⁺ (DMSO is dimethyl sulfoxide) groups via hydrogen-bond inter­actions. The Ce and Na atoms are located on a twofold axis and an inversion centre, respectively.

S1. Comment

Polyoxometalates are currently receiving increasing attention in the domain of solid-state material chemistry, owing to their intriguing structural and topological properties and their many potential applications in catalysis, biology, medicine, photochemistry and magnetism (Pope & Müller, 1991; Pope, 1983). In the past decade, chemists have made great efforts in the design and synthesis of new polyoxometalates. To find suitable subunits and then link them up into one-, two- or even three-dimensional extended networks in appropriate ways remains a great challenge. Recently, a series of octamolybdate-supported complexes with multi-dimensional frameworks have been synthesized by hydrothermal methods (Hagrman et al., 1997, 1998; Wu et al., 2002). To the best of our knowledge, only three octamolybdate-supported compounds with one- or two-dimensional extended structures have so far been reported to be synthesized in a direct route, using [Bu₄N]₄[Mo₈O₂₆] or [Bu₄N]₄[Mo₆O₁₉] as the starting materials (Qin et al., 2004; Chen et al., 2004a,b). We have succeeded in obtaining the title novel octamolybdate-supported compound with a two-dimensional framework, {[Ce(DMSO)₆(H₂O)₂][NaMo₈O₂₆]}_n (DMSO is dimethylsulfoxide), (I), which was also prepared in a direct route but using Na₂MoO₄ as the Mo source. This is the first reported such octamolybdate-based compound with an infinitely extended structure to be synthesized by applying this `one-step' method. It is also the first case of Mo–Na bimetallic oxide chains linked up into a two-dimensional network via hydrogen-bonding interactions between β-[Mo₈O₂₆]⁴⁻ units and coordinated rare earth ions. Please check rephrasing.

Compound (I) consists of an infinite anion chain framework built up of [Mo₈O₂₆]⁴⁻ entities linked via Na ions, and eight-coordinated (six DMSO and two water molecules) Ce atoms as charge compensating cations (Fig. 1). The Ce atom occupies a special position across a twofold axis, and the Na atom lies on an inversion centre at (3/4, 1/4, 1/2).

As shown in Fig. 2, the [Mo₈O₂₆]⁴⁻ moiety is built up of eight edge-sharing MoO₆ octahedra and displays the characteristic β-octamolybdate arrangement, which contains two µ₅-O atoms, O13 and O13ⁱⁱⁱ [symmetry code: (iii) −x + 3/2, −y + 3/2, −z + 1]. The Mo—O bond lengths and O—Mo—O and Mo—O—Mo bond angles among the octamolybdate units are similar to those in other β-[Mo₈O₂₆]⁴⁻ complexes (Luo et al., 2003; Yang et al., 2002; Hagrman & Zubieta, 2000). All Mo sites possess octahedral coordination geometry with different degrees of distortion and exhibit a +VI oxidation state, according to extensive bond-valence sum calculation (Brown & Altermatt, 1984; Brese & O'Keeffe, 1991). Each [Mo₈O₂₆]⁴⁻ unit forms covalent [with Na—O distances of 2.426 (2)–2.445 (2) Å] or weak [with Na—O distances of 2.820 (2)–2.841 (2) Å] interactions with Na⁺ through eight terminal O atoms in opposite directions, thus forming a sandwich-like structure.

The coordination environment around the Ce centre is shown in Fig. 1. Each Ce³⁺ ion is coordinated by eight O atoms, of which six are from DMSO ligands and two from aqua ligands.

It is noteworthy that strong hydrogen-bond interactions exist in the solid-state structure of (I), and these might play an important role in the crystallization of (I). Each coordinated water molecule on the Ce atom forms two O—H···O hydrogen bonds (Table 2) to a µ₂-bridging and a terminal O atom from the adjacent (Mo₈O₂₆)_n chain. Therefore, the structure of (I) is finally extended into a two-dimensional network by strong hydrogen bonds (Fig. 3).

The backbone framework of (I) is similar to that of [NaLa(β-[Mo₈O₂₆]⁴⁻)(DMF)₇]_n (II) (DMF is dimethylformamide; Chen et al., 2004 Which?), although in that compound, the [La(DMF)₇]³⁺ moiety is covalently bound to the infinite one-dimensional chain.

S2. Experimental

Na₂MoO₄ (0.964 g, 4 mmol) was dissolved in H₂O (5 ml) and dimethylsulfoxide (10 ml), and then CeCL₃ (0.67 mmol) in H₂O (2 ml) was added dropwise. The resulting solution was adjusted to about pH3 with 10% hydrochloric acid. After stirring for about 15 min, the mixture was filtered and the filtrate was kept in air at ambient temperature. Orange crystals of the title compound were separated from the mother liquor after one week (yield 45%, based on Ce).

S3. Refinement

The aqua H atoms were located in a difference Fourier map and were refined with restrained O—H distances approximately equal to 0.84 (1) Å and H···H distances approximately equal to 1.4 (1) Å. H atoms bonded to C atoms were positioned geometrically, with C—H distances of 0.96 Å, and allowed to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C). Please check added text.

Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A molecular drawing of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. All H atoms have been omitted for clarity. [Symmetry codes: (i) −x + 1, y, −z + 3/2; (ii) −x + 3/2, −y + 1/2, −z + 1; (iii) −x + 3/2, −y + 3/2, −z + 1; (iv) x, y + 1, z.]
	Fig. 2. A polyhedral representation of the infinite chain in (I). All C and H atoms have been omitted for clarity.
	Fig. 3. A packing diagram for (I), viewed along the c axis. Broken lines indicate hydrogen bonds. Displacement ellipsoids are shown at the 30% probability level. All H atoms have been omitted for clarity, except those engaged in hydrogen bonding.

Poly[diaquahexakis(dimethyl sulfoxide-κO)cerium [(µ₂-hexacosaoxooctamolybdate)sodium]]

Crystal data

[Ce(C2H6OS)6(H2O)2][NaMo8O26]	F(000) = 3540
Mr = 1851.43	Dx = 2.584 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6634 reflections
a = 22.7811 (7) Å	θ = 3.0–27.5°
b = 9.2121 (2) Å	µ = 3.34 mm^−1
c = 22.8913 (6) Å	T = 130 K
β = 97.829 (2)°	Prism, yellow
V = 4759.2 (2) Å^3	0.22 × 0.21 × 0.11 mm
Z = 4

Data collection

Rigaku Mercury CCD area-detector diffractometer	5365 independent reflections
Radiation source: fine-focus sealed tube	5248 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 14.6306 pixels mm^-1	θmax = 27.5°, θmin = 3.5°
ω scans	h = −29→27
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	k = −11→8
Tmin = 0.524, Tmax = 0.693	l = −28→29
16875 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.055	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 15.179P] where P = (Fo^2 + 2Fc^2)/3
5365 reflections	(Δ/σ)max = 0.003
290 parameters	Δρmax = 1.59 e Å^−3
3 restraints	Δρmin = −0.84 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ce1	0.5000	0.41600 (2)	0.7500	0.01128 (6)
Na1	0.7500	0.2500	0.5000	0.0297 (4)
Mo1	0.802281 (9)	0.54411 (2)	0.631042 (9)	0.00971 (6)
Mo2	0.671776 (9)	0.57713 (2)	0.557411 (9)	0.00788 (6)
Mo3	0.730161 (9)	0.63169 (2)	0.439003 (9)	0.00668 (5)
Mo4	0.861733 (9)	0.60356 (2)	0.511859 (9)	0.00861 (6)
O1	0.79975 (9)	0.3656 (2)	0.61080 (9)	0.0185 (4)
O2	0.67575 (8)	0.3981 (2)	0.53810 (8)	0.0129 (4)
O3	0.73131 (8)	0.44910 (19)	0.42926 (8)	0.0113 (3)
O4	0.85246 (9)	0.4220 (2)	0.49704 (8)	0.0149 (4)
O5	0.82988 (9)	0.5467 (2)	0.70415 (8)	0.0174 (4)
O6	0.71947 (8)	0.57654 (19)	0.63262 (8)	0.0107 (3)
O7	0.60332 (8)	0.6009 (2)	0.57701 (8)	0.0132 (4)
O8	0.65804 (7)	0.65505 (19)	0.47483 (7)	0.0089 (3)
O9	0.70419 (8)	0.70554 (19)	0.37000 (8)	0.0105 (3)
O10	0.81389 (7)	0.67609 (19)	0.43793 (7)	0.0090 (3)
O11	0.93116 (8)	0.6437 (2)	0.49771 (9)	0.0158 (4)
O12	0.87187 (8)	0.60089 (19)	0.59602 (8)	0.0105 (3)
O13	0.76467 (7)	0.62679 (19)	0.53331 (8)	0.0085 (3)
O14	0.51709 (10)	0.5114 (3)	0.85003 (10)	0.0283 (5)
O15	0.58105 (9)	0.5915 (2)	0.75486 (10)	0.0246 (5)
O16	0.42905 (9)	0.2892 (2)	0.80427 (9)	0.0185 (4)
O17	0.43715 (11)	0.2238 (3)	0.69388 (10)	0.0396 (7)
C1	0.63906 (15)	0.7809 (3)	0.69944 (14)	0.0252 (6)
H1A	0.6074	0.8030	0.6685	0.038*
H1B	0.6764	0.7975	0.6856	0.038*
H1C	0.6360	0.8421	0.7328	0.038*
C2	0.69680 (15)	0.5893 (4)	0.77620 (14)	0.0308 (7)
H2A	0.7006	0.4936	0.7929	0.046*
H2B	0.6917	0.6583	0.8065	0.046*
H2C	0.7319	0.6129	0.7592	0.046*
C3	0.54620 (14)	0.6034 (5)	0.95711 (14)	0.0320 (8)
H3A	0.5532	0.5093	0.9747	0.048*
H3B	0.5050	0.6279	0.9555	0.048*
H3C	0.5698	0.6743	0.9804	0.048*
C4	0.54779 (17)	0.7841 (4)	0.86603 (17)	0.0347 (8)
H4A	0.5559	0.8033	0.8267	0.052*
H4B	0.5712	0.8475	0.8932	0.052*
H4C	0.5065	0.8006	0.8682	0.052*
C5	0.34028 (12)	0.1930 (3)	0.85352 (13)	0.0205 (6)
H5A	0.3119	0.2639	0.8369	0.031*
H5B	0.3295	0.1586	0.8902	0.031*
H5C	0.3408	0.1131	0.8267	0.031*
C6	0.45280 (15)	0.1197 (4)	0.89636 (16)	0.0344 (8)
H6A	0.4939	0.1449	0.9059	0.052*
H6B	0.4488	0.0423	0.8680	0.052*
H6C	0.4376	0.0889	0.9314	0.052*
S1	0.41224 (3)	0.27390 (8)	0.86617 (3)	0.01752 (14)
S2	0.56565 (3)	0.60142 (8)	0.88463 (3)	0.02073 (15)
S3	0.63411 (3)	0.59532 (7)	0.72049 (3)	0.01420 (13)
H17A	0.4269 (17)	0.201 (4)	0.6587 (7)	0.034 (11)*
H17B	0.4137 (18)	0.192 (6)	0.7160 (18)	0.070 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ce1	0.00929 (10)	0.01402 (10)	0.01096 (10)	0.000	0.00292 (7)	0.000
Na1	0.0440 (11)	0.0194 (8)	0.0308 (10)	0.0180 (8)	0.0233 (8)	0.0136 (7)
Mo1	0.01051 (10)	0.00983 (10)	0.00847 (11)	−0.00013 (7)	0.00012 (8)	0.00232 (7)
Mo2	0.00885 (10)	0.00879 (10)	0.00614 (10)	−0.00189 (7)	0.00151 (7)	0.00060 (7)
Mo3	0.00884 (10)	0.00667 (10)	0.00448 (10)	−0.00073 (7)	0.00075 (7)	−0.00099 (7)
Mo4	0.00944 (10)	0.00944 (10)	0.00676 (10)	0.00173 (7)	0.00043 (7)	−0.00045 (7)
O1	0.0174 (9)	0.0126 (9)	0.0258 (11)	−0.0005 (7)	0.0038 (8)	0.0019 (8)
O2	0.0140 (9)	0.0116 (9)	0.0135 (9)	−0.0015 (7)	0.0034 (7)	0.0007 (7)
O3	0.0141 (9)	0.0095 (8)	0.0105 (9)	−0.0016 (7)	0.0021 (7)	−0.0013 (6)
O4	0.0206 (10)	0.0116 (9)	0.0118 (9)	0.0022 (7)	0.0003 (7)	−0.0008 (7)
O5	0.0179 (9)	0.0231 (10)	0.0105 (9)	−0.0009 (8)	−0.0011 (7)	0.0047 (8)
O6	0.0126 (8)	0.0131 (8)	0.0067 (8)	−0.0013 (7)	0.0023 (7)	0.0015 (6)
O7	0.0123 (9)	0.0160 (9)	0.0114 (9)	−0.0019 (7)	0.0023 (7)	0.0016 (7)
O8	0.0092 (8)	0.0104 (8)	0.0067 (8)	−0.0009 (6)	0.0000 (6)	−0.0008 (6)
O9	0.0131 (8)	0.0108 (8)	0.0075 (8)	−0.0003 (7)	0.0008 (6)	−0.0006 (6)
O10	0.0106 (8)	0.0109 (8)	0.0055 (8)	−0.0001 (6)	0.0011 (6)	−0.0014 (6)
O11	0.0119 (9)	0.0207 (10)	0.0148 (9)	0.0023 (7)	0.0021 (7)	0.0021 (8)
O12	0.0104 (8)	0.0118 (8)	0.0087 (8)	0.0001 (7)	−0.0008 (6)	−0.0001 (6)
O13	0.0087 (8)	0.0091 (8)	0.0078 (8)	−0.0005 (6)	0.0008 (6)	0.0001 (6)
O14	0.0313 (12)	0.0358 (13)	0.0201 (11)	−0.0181 (10)	0.0113 (9)	−0.0133 (10)
O15	0.0221 (11)	0.0291 (12)	0.0262 (12)	−0.0120 (9)	0.0165 (9)	−0.0121 (9)
O16	0.0202 (10)	0.0226 (10)	0.0139 (10)	−0.0040 (8)	0.0068 (8)	0.0020 (8)
O17	0.0379 (14)	0.0703 (19)	0.0121 (11)	−0.0380 (14)	0.0086 (10)	−0.0133 (12)
C1	0.0360 (17)	0.0166 (14)	0.0249 (16)	0.0001 (12)	0.0108 (13)	−0.0025 (12)
C2	0.0243 (16)	0.050 (2)	0.0176 (15)	0.0020 (14)	0.0003 (12)	0.0042 (14)
C3	0.0201 (15)	0.062 (2)	0.0137 (15)	0.0063 (15)	−0.0003 (11)	−0.0008 (15)
C4	0.045 (2)	0.0261 (17)	0.0335 (19)	−0.0046 (15)	0.0090 (15)	−0.0040 (14)
C5	0.0149 (12)	0.0288 (15)	0.0182 (14)	−0.0051 (11)	0.0040 (10)	−0.0007 (12)
C6	0.0256 (16)	0.046 (2)	0.0312 (19)	0.0027 (15)	0.0015 (14)	0.0205 (16)
S1	0.0210 (3)	0.0185 (3)	0.0138 (3)	−0.0052 (3)	0.0051 (2)	−0.0032 (2)
S2	0.0155 (3)	0.0277 (4)	0.0195 (4)	−0.0009 (3)	0.0042 (3)	−0.0068 (3)
S3	0.0151 (3)	0.0170 (3)	0.0115 (3)	−0.0051 (2)	0.0051 (2)	−0.0027 (2)

Geometric parameters (Å, º)

Ce1—O14	2.434 (2)	Mo4—O8^i	2.2975 (17)
Ce1—O15	2.445 (2)	Mo4—O13	2.3392 (17)
Ce1—O16	2.4630 (19)	O14—S2	1.517 (2)
Ce1—O17	2.517 (2)	O15—S3	1.530 (2)
Na1—O2	2.4260 (19)	O16—S1	1.524 (2)
Na1—O3	2.4453 (18)	O17—H17A	0.835 (10)
Na1—O4	2.830 (2)	O17—H17B	0.837 (10)
Na1—O1	2.841 (2)	C1—S3	1.784 (3)
Mo1—O5	1.7060 (19)	C1—H1A	0.9600
Mo1—O1	1.707 (2)	C1—H1B	0.9600
Mo1—O6	1.9152 (18)	C1—H1C	0.9600
Mo1—O12	1.9430 (18)	C2—S3	1.781 (3)
Mo1—O9^i	2.3109 (18)	C2—H2A	0.9600
Mo1—O13	2.4077 (17)	C2—H2B	0.9600
Mo2—O7	1.6946 (19)	C2—H2C	0.9600
Mo2—O2	1.7128 (18)	C3—S2	1.775 (3)
Mo2—O6	1.9065 (18)	C3—H3A	0.9600
Mo2—O8	2.0065 (17)	C3—H3B	0.9600
Mo2—O10^i	2.2971 (17)	C3—H3C	0.9600
Mo2—O13	2.3044 (17)	C4—S2	1.770 (4)
Mo2—Mo3	3.2173 (3)	C4—H4A	0.9600
Mo3—O3	1.6975 (18)	C4—H4B	0.9600
Mo3—O9	1.7474 (17)	C4—H4C	0.9600
Mo3—O8	1.9455 (17)	C5—S1	1.788 (3)
Mo3—O10	1.9542 (17)	C5—H5A	0.9600
Mo3—O13	2.1951 (17)	C5—H5B	0.9600
Mo3—O13^i	2.3120 (17)	C5—H5C	0.9600
Mo4—O11	1.6979 (19)	C6—S1	1.782 (3)
Mo4—O4	1.7139 (19)	C6—H6A	0.9600
Mo4—O12	1.9091 (18)	C6—H6B	0.9600
Mo4—O10	1.9990 (17)	C6—H6C	0.9600
O14^ii—Ce1—O14	137.68 (12)	O11—Mo4—O4	105.53 (10)
O14—Ce1—O15	72.27 (7)	O11—Mo4—O12	101.98 (9)
O14—Ce1—O15^ii	80.05 (8)	O4—Mo4—O12	100.48 (8)
O15—Ce1—O15^ii	97.21 (11)	O11—Mo4—O10	100.39 (8)
O14^ii—Ce1—O16	127.87 (7)	O4—Mo4—O10	96.91 (8)
O14—Ce1—O16	74.25 (7)	O12—Mo4—O10	146.69 (7)
O15—Ce1—O16	146.49 (7)	O11—Mo4—O8^i	91.09 (8)
O15^ii—Ce1—O16	78.07 (7)	O4—Mo4—O8^i	161.75 (8)
O16—Ce1—O16^ii	123.40 (10)	O12—Mo4—O8^i	82.96 (7)
O14^ii—Ce1—O17	76.51 (9)	O10—Mo4—O8^i	72.22 (7)
O14—Ce1—O17	137.83 (7)	O11—Mo4—O13	162.14 (8)
O15—Ce1—O17	149.53 (7)	O4—Mo4—O13	92.08 (8)
O15^ii—Ce1—O17	93.92 (9)	O12—Mo4—O13	77.12 (7)
O16—Ce1—O17	63.72 (7)	O10—Mo4—O13	74.05 (7)
O16^ii—Ce1—O17	77.04 (8)	O8^i—Mo4—O13	71.07 (6)
O17—Ce1—O17^ii	90.59 (15)	Mo1—O1—Na1	126.74 (10)
O2^iii—Na1—O2	180	Mo2—O2—Na1	134.29 (10)
O2^iii—Na1—O3	104.53 (6)	Mo3—O3—Na1	131.35 (9)
O2—Na1—O3	75.47 (6)	Mo4—O4—Na1	128.43 (10)
O2—Na1—O3^iii	104.53 (6)	Mo2—O6—Mo1	115.16 (9)
O3—Na1—O3^iii	180	Mo3—O8—Mo2	108.99 (8)
O2—Na1—O4^iii	71.85 (6)	Mo3—O8—Mo4^i	110.80 (8)
O3—Na1—O4^iii	111.47 (6)	Mo2—O8—Mo4^i	103.27 (7)
O2—Na1—O4	108.15 (6)	Mo3—O9—Mo1^i	114.27 (8)
O3—Na1—O4	68.53 (6)	Mo3—O10—Mo4	109.87 (8)
O4^iii—Na1—O4	180	Mo3—O10—Mo2^i	109.84 (8)
O2—Na1—O1^iii	108.60 (6)	Mo4—O10—Mo2^i	103.52 (7)
O3—Na1—O1^iii	71.20 (6)	Mo4—O12—Mo1	115.25 (9)
O4^iii—Na1—O1^iii	65.25 (6)	Mo3—O13—Mo2	91.26 (6)
O4—Na1—O1^iii	114.75 (6)	Mo3—O13—Mo3^i	104.35 (7)
O2—Na1—O1	71.40 (6)	Mo2—O13—Mo3^i	98.02 (6)
O3—Na1—O1	108.80 (6)	Mo3—O13—Mo4	91.01 (6)
O1^iii—Na1—O1	180	Mo2—O13—Mo4	163.19 (8)
O5—Mo1—O1	105.91 (10)	Mo3^i—O13—Mo4	97.55 (6)
O5—Mo1—O6	102.22 (9)	Mo3—O13—Mo1	162.71 (9)
O1—Mo1—O6	99.12 (9)	Mo2—O13—Mo1	86.38 (6)
O5—Mo1—O12	100.87 (9)	Mo3^i—O13—Mo1	92.94 (6)
O1—Mo1—O12	98.43 (9)	Mo4—O13—Mo1	86.52 (6)
O6—Mo1—O12	145.78 (7)	S2—O14—Ce1	134.47 (12)
O5—Mo1—O9^i	90.60 (8)	S3—O15—Ce1	129.51 (12)
O1—Mo1—O9^i	163.48 (8)	S1—O16—Ce1	141.10 (12)
O6—Mo1—O9^i	77.46 (7)	Ce1—O17—H17A	137 (3)
O12—Mo1—O9^i	77.38 (7)	Ce1—O17—H17B	108 (4)
O5—Mo1—O13	160.74 (8)	H17A—O17—H17B	112 (4)
O1—Mo1—O13	93.32 (8)	S3—C1—H1A	109.5
O6—Mo1—O13	75.01 (7)	S3—C1—H1B	109.5
O12—Mo1—O13	74.84 (7)	H1A—C1—H1B	109.5
O9^i—Mo1—O13	70.16 (6)	S3—C1—H1C	109.5
O7—Mo2—O2	105.99 (9)	H1A—C1—H1C	109.5
O7—Mo2—O6	101.14 (8)	H1B—C1—H1C	109.5
O2—Mo2—O6	100.76 (8)	S3—C2—H2A	109.5
O7—Mo2—O8	99.92 (8)	S3—C2—H2B	109.5
O2—Mo2—O8	96.21 (8)	H2A—C2—H2B	109.5
O6—Mo2—O8	148.03 (7)	S3—C2—H2C	109.5
O7—Mo2—O10^i	89.44 (8)	H2A—C2—H2C	109.5
O2—Mo2—O10^i	162.29 (8)	H2B—C2—H2C	109.5
O6—Mo2—O10^i	84.32 (7)	S2—C3—H3A	109.5
O8—Mo2—O10^i	72.10 (7)	S2—C3—H3B	109.5
O7—Mo2—O13	161.09 (8)	H3A—C3—H3B	109.5
O2—Mo2—O13	92.68 (8)	S2—C3—H3C	109.5
O6—Mo2—O13	77.75 (7)	H3A—C3—H3C	109.5
O8—Mo2—O13	74.56 (7)	H3B—C3—H3C	109.5
O10^i—Mo2—O13	71.66 (6)	S2—C4—H4A	109.5
O7—Mo2—Mo3	134.74 (6)	S2—C4—H4B	109.5
O2—Mo2—Mo3	83.71 (6)	H4A—C4—H4B	109.5
O6—Mo2—Mo3	120.73 (5)	S2—C4—H4C	109.5
O8—Mo2—Mo3	34.88 (5)	H4A—C4—H4C	109.5
O10^i—Mo2—Mo3	79.17 (4)	H4B—C4—H4C	109.5
O13—Mo2—Mo3	43.01 (4)	S1—C5—H5A	109.5
O3—Mo3—O9	106.05 (9)	S1—C5—H5B	109.5
O3—Mo3—O8	101.18 (8)	H5A—C5—H5B	109.5
O9—Mo3—O8	97.85 (8)	S1—C5—H5C	109.5
O3—Mo3—O10	99.97 (8)	H5A—C5—H5C	109.5
O9—Mo3—O10	96.78 (8)	H5B—C5—H5C	109.5
O8—Mo3—O10	149.76 (7)	S1—C6—H6A	109.5
O3—Mo3—O13	95.68 (8)	S1—C6—H6B	109.5
O9—Mo3—O13	158.26 (8)	H6A—C6—H6B	109.5
O8—Mo3—O13	78.32 (7)	S1—C6—H6C	109.5
O10—Mo3—O13	78.30 (7)	H6A—C6—H6C	109.5
O3—Mo3—O13^i	171.30 (8)	H6B—C6—H6C	109.5
O9—Mo3—O13^i	82.62 (7)	O16—S1—C6	104.58 (15)
O8—Mo3—O13^i	78.02 (7)	O16—S1—C5	103.24 (13)
O10—Mo3—O13^i	77.80 (7)	C6—S1—C5	98.41 (16)
O13—Mo3—O13^i	75.65 (7)	O14—S2—C4	105.48 (17)
O3—Mo3—Mo2	88.36 (6)	O14—S2—C3	103.69 (15)
O9—Mo3—Mo2	133.98 (6)	C4—S2—C3	97.84 (18)
O8—Mo3—Mo2	36.14 (5)	O15—S3—C2	104.10 (15)
O10—Mo3—Mo2	124.02 (5)	O15—S3—C1	104.14 (14)
O13—Mo3—Mo2	45.73 (4)	C2—S3—C1	98.57 (17)
O13^i—Mo3—Mo2	86.03 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O17—H17B···O5^iv	0.84 (1)	2.32 (4)	2.974 (3)	136 (5)
O17—H17A···O12^iv	0.84 (1)	2.00 (2)	2.758 (3)	151 (4)

Symmetry code: (iv) x−1/2, y−1/2, z.